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San Jacinto QAPP

1. EPN OP EPA 8141 3L ses Unpreserved 7 Ethion OP EPA 8141 3L 1 owed Unpreserved 7 8141 3L Ed Unpreserved 7 Famphur OP EPA 8141 3L IE 07 Unpreserved 7 Fenitrothion OP EPA 8141 3L 1 pond Unpreserved 7 Fensulfothion OP EPA 8141 3L 1 poo Unpreserved 7 Fonophos OP EPA 8141 3L 1 pd Unpreserved 7 Fenthion OP EPA 8141 3L prd Unpreserved 7 Leptophos OP EPA 8141 3L 1L T Unpreserved 7 Malathion OP EPA 8141 3L yu Unpreserved 7 Merphos OP EPA 8141 3L jo Unpreserved 7 8141 3L poeta Unpreserved 7 Monocrotophos OP EPA 8141 3L 1 um Unpreserved 7 Naled OP EPA 8141 3L 1 md Unpreserved 7 Parathion ethyl EPA 8141 3L 1 pod Unpreserved 7 Parathion methyl OP EPA 8141 3L E un Unpreserved 7 Phorate OP EPA 8141 3L 1 pe Unpreserved 7 Phosmet OP EPA 8141 3L ps Unpreserved 7 Phosphamidon OP EPA 8141 3L 1 ess Unpreserved 7 Ronnel OP EPA 8141 3L 1 rou Unpreserved 7 0 SRM 3k Sulfotepp OP EPA 8141 3L em Unpreserved 7 TEPP OP EPA 8141 3L 1 pou Unpreserved 7 Terbufos OP EPA 8141 3L Unpreserved 7 Thionazin Zinophos OP EPA 8141 3L f mt Unpreserved 7 on Protothiofos EPA 8141 3L 1L zm Unpreserved 7 Trichlorfon OP EPA 8141 3L 1 ps Unpreserved 7 Trichloronate OP EPA 8141 3L 1 ps Unpreserved 7 Lake Elsinore amp Canyon L
2. ccccccccccccccssssssceeececeeeessnseceeeeeceessssaeceeeeeees 31 B5 QUALITY CONTROL REQUIREMEN TS ersten enters a a as 36 INSTRUMENT EQUIPMENT TESTING INSPECTION AND MAINTENANCE REQUIREMENTS NI neret aieo 36 B7 INSTRUMENT CALIBRATION AND FREQUENCY eese eene emen 36 B8 INSPECTION ACCEPTANCE REQUIREMENTS FOR SUPPLIES AND CONSUMABLES 37 B9 NON DIRECT MEASUREMENTS essere eene Rhe eiii resist 37 B10 DATA MANAGEMENT 0 ccccccccccccccccccccccccccscscccscsesescsescsescscsesesesesesesesssssssesesesesesesesesesesesesesenescs 38 SECTION C ASSESSMENT OVERSIGHT ELEMENTS enne 39 Cl ASSESSMENT AND RESPONSE ACTIONS eeee ene eene enne stesse 39 C2 REPORTS TO MANAGEMENT rere 39 SECTION D VALIDATION AND USABILITY e 40 DI DATA REVIEW VALIDATION AND VERIFICATION REQUIREMENTS 40 D2 VALIDATION AND VERIFICATION METHODS esee eem nemen nne enis 40 D3 RECONCILIATION WITH DATA QUALITY OBJECTIVES eee 40 SECTION REFERENCES oue emo teu Eu ed 41 1 REFERENCES uA oum etie 41 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 4 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE TABLES Table 1 Responsible Personnel QAPP Update and Maintenance eene 10 Table 2 San Jacinto Watershed Paramete
3. 0 5 C for 15 minutes or until dissolved A loop full of the suspension is streaked onto a Standard Methods agar slant and kept at 4 for up to a month LSB BGB EC EC MUG Enterobacter aerogenes Pseudomonas aeruginosa NA Escherichia coli Enterococcus faecalis NA NA NA NA Revision 6 0 Page 4 of 9 B02 MTF 8 0 Sample Collection Preservation and Storage 8 1 Samples are collected in sterile 120 mL containers containing Na2S2O3 for chlorine removal 8 2 Samples must be kept cold 10 C from sampling until analysis If a sample arrives lt 30 and on ice it is assumed that the cooling process has begun If a sample arrives gt 30 even if it is on ice or gt 10 C without ice the client is advised that the sample temperature may affect test results 8 3 Samples must be analyzed within 30 hours for drinking water and within 6 hours for wastewater 9 0 Inoculation of Drinking Water Samples 9 10 milliliters of sample is transferred to each of 10 tubes containing 10 mL of double strength sterile broth 9 2 All broth tubes are placed in incubators The broth tubes are allowed to incubate for 24 2 hours examined and then incubated for an additional 24 3 hours if needed at 35 C 0 5 9 3 Note Heterotrophic plate counts are also set up at this time see SOP B07 10 0 Inoculation of non drinking waters such as effluents stormwaters source waters and other sur
4. 10 10 10 10 5 of 8 6 Some samples may be difficult to filter In order to maximize sample size try one of the following If possible do not use less than 10 ml of sample 10 6 1 A bigger filtration apparatus may be necessary for samples that are not high in salts but contain a great deal of suspended material It is recommended that the filter time not exceed 10 minutes 10 6 2 Change filter papers as often as necessary to filter sample ensuring that each filter is rinsed thoroughly 7 After the sample has filtered through make sure that the filter is completely dry prior to turning off the pump Drips should be at least 5 seconds apart and the filter must be visually dry Rinse into the filtrate the filter paper and cylinder with D I water Pour filtrate into the evaporating dish Rinse flask with a small amount of D I water Add the rinse to the evaporating dish with the filtrate 8 After each sample rinse all apparatus three times with deionized water 9 Place samples on water bath until they are dry After samples are dry put in 180 C oven for 1 5 hours which is sufficient time to bring the sample to constant weight as proven by an annual constant weight study Wipe down the outside of each dish prior to placing them in the oven 10 Cool dishes in a desiccator at least half an hour until room temperature Weigh dishes Record weight 11 Wa
5. 12 7 If the sample is a solid Tl Add deionized water in a 1 10 ratio with the soil I e 5g of sample to 50mL water or any ratio that is convenient I2 7 2 Allow leaching for 1 hour with frequent stirring T2159 Follow the procedure in section 12 1 LINZ MET 13 0 Reading Samples T3 Before reading samples on the spectrophotometer zero instrument on the following blank 13 021 Blank 10mL of nanopure water to which 1 6mL of P Reagent have been added T3452 Read samples one at a time rinsing blotting and wiping the cuvette in between each one Revision 5 0 I27 OP Page 9 of 9 14 0 Calculations 14 1 Compare each sample absorbance to a current graph 14 2 Multiply concentration by Dilution Factor if 10mL were not used 14 3 Read to 2 significant figures 14 4 The reporting limit is 0 05 mg L 14 5 All results are reported as ortho phosphate phosphorus the sample is filtered no distinction is made for dissolved versus total since 40 CFR part 136 Table instructs all ortho phosphates to be filtered immediately 15 0 Definitions SOP 015 SOP Definitions 16 0 Corrective Action For Out of Control Or Unacceptable Data 16 1 See SOP Q06 Corrective Action 17 0 Pollution Prevention and Waste Management T3 e See SOP S05 Neutralization Procedure for Acid and Alkaline Waste 17 2 SOP S07 Pollution Prevention 17 23
6. Quality Control Note See also ESB SOP 001 for general QC requirements 9 1 A Laboratory Control Sample is analyzed with each batch of 20 or fewer samples per matrix type Compare the Laboratory Control results to the acceptance ranges If the results are not within the acceptance ranges of 90 110 the analysis is considered to be out of control and the problem must be corrected before the analysis proceeds 9 az Matrix Spikes MS and MSD are analyzed with each batch of 20 or fewer samples per matrix type Calculate the percent recoveries of the spikes by the following equation Spiked sample sample 1 X 100 If the spike recovery does not fall within acceptance ranges of 80 120 max RPD of 20 for aqueous samples and historically generated limits for solid samples the spike must be re analyzed If the second spike still does not fall within acceptance ranges the client s results are flagged 9 3 The Midpoint Check is analyzed with each batch of 20 or fewer samples It must fall within the same criteria as the lab control or the validity of the curve is in question If the midpoint check is remade and it is still out of range a new curve may have to be drawn 9 4 An MDL study is completed whenever major equipment or procedural changes are made Standards are Spiked at the reporting limit or 2 5 5 times the Revision 5 0 I22 NO2 Pag
7. 1 Laboratory Analyses Standard methods APHA 1998 will be used for analysis of all water samples Table 1 summarizes the method to be used for each analyte as well as the detection limit operating range and calibration method The analyst is referred to Standard Methods 1998 for specific method protocol Table 1 Methods to be used for analysis of water samples Analytical Limit of Operating Calibration Parameter TERME aramete Method Quantification Range Method FIELD Air Sat d dissolved oxygen DO 4500 O 0 1 mg L 0 1 20 mg L Water water temperature 2550 B 0 01 C 4 35 C specific conductance 2510B 0 01 mS cm 0 01 50 mS cm Standards pH 4500 H 0 01 2 12 Buffers turbidity 2130 0 1 NTU 0 1 100 NTU Standards water clarity Secchi depth N A 0 05 m 0 05 30 m i oxidation reduction potential ORP 2580 B 1mV 300 800 mV Standards Laboratory ammonia nitrogen NH4 N 4500 NH3 0 04 mg L 0 04 4 mg L Standards nitrate nitrite nitrogen 4500 NO3 F 0 04 mg L 0 04 4 mg L Standards total nitrogen TN 4500 N 0 04 mg L 0 04 4 mg L Standards soluble reactive phosphorus SRP 4500 P G 0 01 mg L 0 01 1 mg L Standards total suspended solids TSS 2540 D 5 mg L 5 100 mg L biochemical oxygen demand BOD 5210 B 3 mg L 3 100 mg L chemical Oxygen demand COD 5220D 10 mg L 10 1000 mg L Standards ch
8. 5 1 Normal accepted laboratory safety practices should be followed during reagent preparation and instrument operation No known carcinogenic materials are used in this method 5 2 See SOP S01 Concentrated Acids and Bases SOP S02 Compressed Gas Cylinder Handling SOP S03 Spill Control Policy 6 0 Apparatus and Materials 6 1 Balance Analytical capable of accurately weighing to the nearest 0 0001 g 6 2 Ion chromatograph Analytical system complete with ion chromatograph and all required accessories including syringes analytical columns compressed gasses and detectors 6 2 1 IC Dionex DX 120 1 and 2 Pump Rate 2 0 mL min Eluent as specified in 7 3 1 Sample Loop 25 uL 6 2 2 Data Handling Pentium Processor with Peak Net software on Windows NT platform 6 2 3 Printer HP Laser Jet 2100 6 2 4 Autosampler Alcott Micromeritics 728 708 6 2 5 Anion guard column AG4A 4mm Dionex Guard Column A protector of the separator column If omitted from the system the retention limes will be shorter Usually packed with a substrate which is the same in the separator column 6 2 6 Anion separator column AS 4A 4mm Dionex Column 6 2 7 Anion suppressor column Anion self regenerating ASRS 11 6 2 8 Detector Conductivity cell 6 3 Standard laboratory glassware volumetric flasks beakers graduated cylinders pipets Note All glassware is cleaned immediately prior to and after use by thorough rinsing with three portions
9. Rampl 25 C min Templ 165 Second Hold 5 min Ramp2 5 C min Temp2 290 Hold2 0 min Constant flow 2mL min Detector Nitrogen phosphorus NPD Air flow 55mL min H flow 3 3mL min Helium make up 3mL min 6 4 2 Column 2 Confirmation detector MSD 30m long x 0 25mm I D Equity SPB 5 bonded fused silica column 0 25um film thickness Helium carrier gas flow 15 established at 40mL min linear velocity The injection volume was 2uL The injector temperature must be 250 C and the detector temperature was 330 C 6 4 3 Detector Mass Spectrometer scanning 35 450 m e EM 82 Autotune Setting Threshold 250 Aux 2 300 C Solvent delay 2 0 min Revision 4 1 Page 6 of 16 O53 8141 7 0 REAGENTS and CONSUMABLE MATERIALS 7 1 Solvents Acetone methylene chloride methyl tert butyl ether 7 2 Reagent Water Reagent water Nanopure is defined as a water that is reasonably free of contamination that would prevent the determination of any analyte of interest 7 3 Stock Standard Solutions Stock standard solutions are purchased as certified solutions Solutions are stored in sealed vials protected from light at 4 Manufacturer expiration dates are observed Stock standards will be replaced sooner if comparison with QC samples indicate a problem Two sources are purchased one for calibration standards and the other as a Lab Control and Matrix Spike source 7 4 Working Standard Solu
10. remake If it is not within range repour Ens If it is still out examine the or instrument for problems The calibration may have to be take accepta 7 4 3 Shake Wipe th there a the tur pointin higher must be previou range be repeated Sample results may not n until a Lab Control falls within t nce ranges the sample and pour it into the cell e cell with lens paper to make sure re not smudges then put the cell in bidity meter with the line on the ce g foreword If the sample reading i than the 0 80 range the calibration checked using a lab control from t S table that encompasses the sample Record the lowest stabilized readin befor before the readings begin to climb back up sample particles have settled he to i 1 S he RS g or 7 4 4 Do not dilute the sample Standard Methods 20th Edition Method 2130B 4a and Hach Mode 2100N T above 4 the qua urbidity Meter Manual 2 3 8 Readin 1 gs 000 are reported as gt 4000 NTU using lifier GE Calculation and Reporting Requirements 8 1Results are reported NTU s 8 2Report results to 2 significant figures 8 3Reporting Limi t RL 0 2 NTU QA QC Requirement See also ESB SO S 001 for general QC requirements Revision 5 0 I36 Turbidity Page 6 of 7 9 1 The 0 85 NTU LCS serves as an Initial Calibration check analyzed at the beginning of the analysis An
11. 1 3 2 1 3 3 Matrix spikes are performed on appropriate analyses Check the SOP for the analysis in question to determine if a matrix spike is to be performed Matrix spikes are performed at a frequency that meets data quality objectives or specified test method requirements The laboratory fortifies matrix spikes with all reportable components with the following exceptions 1 3 3 1 The method specifies specific spiking components 1 3 3 2 Components that interfere with each other may be excluded or handled separately 1 3 3 3 Test methods with a long list of target analytes will spike only a core group of compounds This core group of spiking compounds represents all chemistries elution Revision 7 0 Page 4 of 14 1 3 4 1 3 5 1 3 6 1 3 7 1 3 8 001 patterns and masses The core group must consist of the following number of spiking compounds of target analytes of spiking compounds in MS mix 1 10 10096 11 20 80 at least 10 compounds 220 16 compounds Every two years a set of 4 MS s or 2 MS MSD s is analyzed containing all other NELAP analytes per method per matrix Since historical data is unavailable for these analytes results are simply noted Samples for matrix fortification are chosen at random rotated among clients Samples that pose unusual obvious matrix problems however are rejected as an unrepresentative choice for the batch Percent Recovery is calculated by computer as ind
12. calculations must be manually entered on the data review screen Click Edit and enter results on the appropriate line When finished move curser off last entry and click Save Ic CAL Zr ICA Mineral Balances Equation 1 me L Ca Mg Na K total cations Equation 2 me L Total Alkalinity SO4 CH NO3 N F total anions Equation 3 Calculated TDS by summation mg L Ca Mg Na K Cl S04 NO3 F Si02 0 6 Total Alkalinity as CaCO3 The measured TDS may be higher than the calculated TDS because a significant contributor may not be in the calculation Equation 4 Acceptance Criteria Difference 100 X total cations total anions total cations total anions Difference should be 5 Revision 4 0 Q10 Page 4 of 6 Equation 5 1 total cations total anions x 50 Both the total anion and total cations should be 1 100 of the measured EC value The calculated EC is expected to be within 10 of the measured EC Thus Equation 6 0 9 u lt calculated EC lt u 1 1 If the ratio of TDS to conductivity falls below 0 55 the lower ion sum is suspect and reanalyzed If the ration is above 0 7 the higher ion sum is suspect and reanalyzed If reanalysis causes no change in the lower ion sums an unmeasured constituent such as nitrite or organic acids may be present at significant levels If poorly disassociated calcium and sulfate ions are present the TDS may be higher than the EC
13. mg L Nitrite nitrogen mg L 11 8 Report all results to two significant figures 12 0 Definitions See SOP Q15 SOP Definitions Revision 5 0 145 Page 10 of 10 13 0 Pollution Prevention and Waste Management 13 1 Waste Disposal 13 1 1 Instrument waste is placed in the KjN waste barrel 13 1 2 Sample waste after digestion is placed in the High Acid Concentration Waste barrel 13 2 See also SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP S07 Pollution Prevention 14 0 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 15 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts References Standard Methods for the Examination of Water and Wastewater AWWA WPCF 18 Edition 4500 O Standard Methods for the Examination of Water and Wastewater APHA AWWA WPCF 20 Edition 4500 0 SEAL AQ2 Method No EPA 125 A Rev 3 EPA Method 351 2 1993 Methods for the Chemical Analysis of Waters and Wastes Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 09 18 06 Revision 5 0 153 NH3 Page 1 of 10 Standard Operating Procedure Edward S Babcock amp Sons SM 4500 NH Nitrogen Ammonia Colorimetric Automated Phenate Effective Date __ 09 22
14. read 4 0 2 5 Wait for the ready light 9 6The instrument is now calibrated and the electrode may be rinsed dried and placed in the first sample Pull electrode in and out of tube with a slight bouncing action to ensure that no air is trapped under the electrode The probe is not placed in successive portions of sample and samples are not stirred during analysis as specified in the method Samples are thoroughly mixed prior to subsampling In the event that unusual variations are observed samples are repoured and reanalyzed Revision 5 0 Page 4 of 8 10 0 7 If samp 125 le reading is less than 5 or greater than 9 and this value is not confirmed by historical data or sample id place probe in buffer that most a osely matches the sample value to standardize electrode Then pour a fresh aliquot to verify result Finish by placing electrode into buffer and a proceeding 8 Rinse and dry the electrode between each sample 9 Record the answers in the EC pH log book to the nearest 0 1 units lt LO be duplicates or two runs of the same sample th th tu in T2 The first two runs in each set of samples sh 7 llowing electrode to return to neutral before ould LE e two duplicate readings are not within 0 1 of each other repour the sample and take another reading If they are still out of range reread e L
15. 3 2 4 Standards are made at levels that typically bracket expected concentrations but do not exceed instrument linearity Calibration Acceptance Calibrations are accepted based on individual method requirements Calibration curves or response factors are printed on hard copy or stored electronically If the method does not specify acceptance criteria a linear curve must have a correlation coefficient r as specified below and a nonlinear curve must have a coefficient of determination specified below Linear Nonlinear Inorganic methods gt 0 995 r gt 0 99 500 600 methods gt 0 99 gt 0 98 8000 methods gt 0 99 r gt 0 99 Note The run may reprocessed based a later calibration as long as the reprocessed run contains method required QC that is acceptable under the new calibration 34 3 5 3 6 3 7 Initial Calibration Verification Standard ICV Initial calibrations are validated by quality control samples obtained from a noncalibration source and analyzed during the analytical run This may be either the LCS or a separate ICV as long as it represents a second source for every analyte of interest Results must be within ICV acceptance ranges specified in the analytical SOP If the ICV is not acceptable see SOP Q06 for corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager Initial calibration is used directly for quantitation I
16. 4500 NH3 1998 Chlorophyll a samples will be analyzed using an in situ flourometer Total and dissolved Fe concentrations will be quantified on unfiltered samples and filtered samples acidified with metals grade HNO3 using the inductively coupled plasma method 3120 B on a Perkin Elmer Optima 3000 DV or equivalent TOC and DOC Lake Elsinore only will be measured on unfiltered and filtered water samples respectively following standard method 5310 C using a Shimadzu Model TOC V total organic carbon analyzer or equivalent TDS and TSS concentrations will be determined using standard methods 2540 C and 2540 D APHA 1998 Sample Disposal Procedures Field equipment is used at the sampling location therefore sample disposal is not necessary Babcock SOP A06 can be found in the Appendix A and contains sample disposal procedures Laboratory Turnaround Times Typical laboratory turnaround time is two weeks from time of analysis Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 32 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Table 10 Anayltical Methods San Jacinto Watershed Nutrient TMDL and SJRIPP Monitoring Program Method Calibration Parameter Analysis SOP Detection Operating Range Limit Method turbidity SM2130B 0 13 NTU 0 2 4000 NTU 4 point curve water temperature SM 2550B 0 1 C 4 35 C N
17. 6 3 summarizes the recommended operating conditions for the gas chromatograph 11 2 2 The system may be calibrated daily The standards and extracts must be in MTBE 11 2 3 Add 8uL of the internal standard solution to the sample extract QC and calibration standards seal and shake to distribute the internal standard 11 2 4 Inject 2uL of the sample extract Record the resulting peak size in area units 11 2 5 If the response for the peak exceeds the working range of the system dilute the extract and reanalyze 11 2 6 Watch for possible carry over Studies have shown that no carry over occurs when a blank is run after the high calibration standard 10 Rerun samples at or above the reporting limit following a sample at this concentration Be mindful of carry over that may also occur during the extraction process 12 0 IDENTIFICATION OF ANALYTES 12 1 Identify a sample component by comparison of its retention time to the retention time of a reference chromatogram If the retention time of an unknown compound corresponds within limits to the retention time of a standard compound then identification is considered positive 12 2 Retention time windows The computer software allows the setting of retention time windows This is used to make identifications unless experience shows that the window requires adjustment Three times the standard deviation of a retention time within a period of 72 hours can be used to calculate a suggested
18. LFB Laboratory Control Sample LCS or Blank Spike BS is prepared by fortifying an aliquot of the laboratory reagent blank with all analytes to a suitable concentration approximately 100 times their respective MDL 200 uL of an Intermediate standard is spiked into 5 mL of Nanopure water See batch standard log for individual metal concentrations The LFB must be carried through the same entire preparation scheme as the samples including sample digestion when applicable 77 4 The rinse blank is prepared by acidifying reagent water to 5 nitric acid and 2 5 hydrochloric acid 7 8 Instrument Performance Check IPC CCV Solution The IPC is a mixed standard obtained from a reputable vendor This standard is the same source as the calibration stock standards The IPC solution is stored in a plastic bottle and analyzed as needed to meet data quality needs Section 9 5 5 See standard log for recipe 7 9 Quality Control Sample QCS The QCS is a noncalibration source mixed standard containing all certified metals This standard is used to initially prove method capability section 9 2 3 demonstrate continuing acceptable instrument performance semiannually via the Performance Testing program Revision 4 1 7 200 7 Page 8 of 21 section 9 4 and to verify calibration standards after new standard preparation section 9 5 6 See standard log for recipe 7 10 Initial Calibration Verification ICV The ICV is a mixed standa
19. LRB is analyzed This blank is analyzed every 20 samples per matrix type The analyst analyzes Nanopure water for aqueous batches and sand for nonaqueous batches If within the retention time window of any analyte of interest the LRB produces a peak above the reporting limit that would prevent the determination of that analyte determine the source of contamination and eliminate the interference before processing samples Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured raw concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a note 8 3 INITIAL DEMONSTRATION OF CAPABILITY 8 3 1 8 3 2 8 3 3 Each laboratory must demonstrate initial proficiency with each sample preparation and determinative method combination it utilizes by generating data of acceptable accuracy and precision for target analytes in a clean matrix The laboratory must also repeat the following operations whenever new staff are trained or significant changes in instrumentation are made A representative fortified concentration of 10 to 50 times the method detection limit or midrange is used A 10ppb sample concentration is prescribed by the method for single component analytes and 50ppb for multiple but this value may not fall within the working range of the instrument A sample concentrate in methanol conta
20. MATRIX MOLECULAR IONS BROMIDE 12 Molecular Ion Mass 81BrH 82 79BrO 95 81BrO 97 81BrOH 98 Ar81Br 121 Element Interference Se Mo Mo Mo Sb Revision 3 0 M12 200 8 Page 22 of 26 CHLORIDE Molecular Ion Mass Element Interference 35 1 51 V 35CIOH 52 Cr 37C1O 53 Cr 37ClOH 54 Cr Ar35Cl 75 As Ar37Cl 77 SULFATE Molecular Ion Mass Element Interference 325 48 325 49 345 50 Cr 34SOH 51 V 502 52 64 Zn Ar32S 72 Ar34S 74 PHOSPHATE Molecular Ion Mass Element Interference PO 47 POH 48 PO2 63 Cu ArP 71 GROUP I METALS Molecular Ion Mass Element Interference ArNa 63 Cu ArK 79 ArCa 80 MATRIX OXIDES Molecular Ion Mass Element Interference TiO 62 66 Ni Cu Zn ZrO 106 112 Ag Cd MoO 108 116 Cd method elements or internal standards affected by the molecular ions Oxide interferences will normally be very small and will only impact the method elements when present at relatively high concentrations Some samples of matrix oxides are listed of which the analyst should be aware It is recommended that Ti and Zr isotopes are monitored in solid waste samples which are likely to contain high levels of these elements Mo is monitored as a method analyte Revision 3 0 M12 200 8 Page 23 of 26 TABLE 3 INTERNAL STANDARDS AND LIMITATIONS OF USE Internal Standard Mass Possible Limitation 6Lithium 6 a Scandium 45 polyatomic ion interference Germanium 72 Yttriu
21. Please refer to the report Appendices A amp B for available laboratory SOPs laboratory data will be entered into the TASK FORCE database and filed in the TASK FORCE archives along with related materials such as field forms chain of custody forms photographs correspondence etc The SJW Quality Assurance Manager will review all laboratory data as submitted for the San Jacinto Watershed Nutrient Monitoring Program and will request additional re analysis as warranted The LE Quality Assurance Manager will review all laboratory data as submitted for the Lake Elsinore Nutrient Monitoring Program and will request additional re analysis as warranted The CL Quality Assurance Manager will review all laboratory data as submitted for the Canyon Lake Nutrient Monitoring Program and will request additional re analysis as warranted The SJRIPP Quality Assurance Manager will review all laboratory data submitted for the SJRIPP Monitoring Program and will request additional re analysis as warranted The appropriate Quality Control Officer for each component of the San Jacinto QAPP will review laboratory data to determine compliance with the quality control limits established for precision bias completeness and representativeness If criteria are not met the Quality Control Officer will request that samples be re analyzed if holding times allow In coordination with the Laboratory Manager if results from the re testing are within QC limits t
22. Preservation by addition of conc H2SO0 to a pH lt 2 and refrigeration at 4 Samples must be analyzed within 28 days Revision 5 0 153 NH3 Page 2 of 10 4 0 Interferences 4 Calcium and magnesium ions may be present in concentrations sufficient to cause precipitation problems during analysis A 7 596 EDTA solution is used to prevent the precipitation of calcium and magnesium ions from river water and industrial waste For sea water a sodium potassium tartrate solution may be used See SM 4500 NH3 for recipe 4 2 Sample turbidity and color may interfere with this method Turbidity must be removed by filtration prior to analysis Sample color that absorbs in the photometric range used will also interfere If necessary sample is diluted 4 3 Urea and cyanates will hydrolyze on distillation at pH of 9 5 4 4 Dechlorination is not necessary since the colorimeteric analysis will detect chloramines formation 4 4 Marked variation in acidity and alkalinity are eliminated by sample preservation with H2SO4 The pH is then checked to ensure that it is lt 2 Due to the reducing nature of this environment residual chlorine is not expected to be a problem The sample is neutralized prior to analysis by the addition of the first reagent that is a NaOH buffer 4 4 Distillation is required for all samples under the NPDES permit program AII other samples are filtered and may be distilled if the sample presents special matrix
23. San TASK FORCE 951 354 4221 Jacinto Watersheds Administrator 951 352 3422 fax Authority mnorton sawpa org Rick Whetsel Lake Elsinore amp San Monitoring Program 951 354 4222 Jacinto Watersheds Manager 951 352 3422 fax Authority rwhetsel 9 sawpa org Steve Clark Riverside County Flood San Jacinto Watershed 951 955 1346 Control amp Water Quality Assurance 951 788 9965 fax Conservation District Manager seclark 9 co riverside ca us Sarah Garber Elsinore Valley Lake Elsinore and 626 568 6910 Municipal Water Canyon Lake Nutrient Sarah M Garber us mwhglobal com District Quality Assurance Manager Dr Michael Anderson University of Riverside Canyon Lake Monitoring Program Manager 951 827 3757 951 827 3993 fax michael anderson Q ucr edu Pat Boldt San Jacinto River San Jacinto Watershed 951 808 853 Watershed Council Component of the 951 764 9635 fax Santa Ana Integrated mpboldtGaol com Watershed Plan Administrator Alex Gann Riverside County San Jacinto River 951 955 1180 Improvement and Protection Program 951 955 1105 fax agann Grceo org Administrator Hope Smythe Santa Ana Regional TMDL Program 951 782 4493 Water Quality Control Manager 951 782 6288 fax Board hsmythe waterboards ca gov David Woelfel Santa Ana Regional Grant Manager SJRIPP 951 782 7960 Water Quality Control 951 782 6288 fax Board dwoelfel waterboards ca gov Pavlo
24. The sample is then diluted for the determination of the remaining elements 11 4 8 Analytical Summary Refer to ELAN 6000 or 9000 manual 11 4 8 1 Fill Autosampler tray with blanks standards and samples as desired Under the sample portion of the method program fill out the sample table to match the Autosampler positions 11 4 8 2 Analyze the calibration blank 11 4 8 3 Analyze the calibration standard 10 ug L 0 5ug L Hg 11 4 8 4 Analyze the SOug L Hg 1ug L Make certain QC is acceptable Table 8 and sec 9 2 3 11 4 8 5 Analyze CCV 10 ug L 0 5 ug L Hg Make certain QC is acceptable 10 11 4 8 6 Analyze CCB Make certain QC is acceptable no analytes found at gt 11 4 8 7 Analyze a 1 ppb 0 25 ppb Hg RL std Make certain QC is acceptable 50 15090 11 4 8 8 Analyze 100 ug L 2ug L Hg linearity check standard Linearity is dependent of 90 110 recovery 11 4 8 9 Analyze the LRB Make certain QC is acceptable LRB values must not exceed 12 the reporting limit for all metals of concern 11 4 8 10 Analyze LFB DW 25ug L Hg 2 5ug L WW 200ug L Hg 4ug L Make certain QC is acceptable 31596 11 4 8 11 Analyze samples and MS MSD samples 11 4 8 12 Analyze CCV CCB QCS and CCB2 after every 10 samples and at end of run CCB criteria are the same as in section 11 4 8 9 CCV criteria are 10 for re calibration flag and 15 for re analysis flag See sec 9 3 6 QCS and CCB2 are evaluate
25. The acceptance criterion is as follows Equation 7 Measured TDS Calculated TDS 0 55 to 0 7 and or 0 55 to 0 7 Measured EC Calculated EC Reference Standard Methods for the Examination of Water and Wastewater APHA AWWA WEF 18th edition Demand Ratios A general rule of thumb is BOD 04 to 0 6 of COD TOC z 0 4 approx of COD TOC z 0 6 approx of BOD Nutrient Relationships Total Nitrogen Organic Nitrogen Inorganic Nitrogen Inorganic Nitrogen NO3 N NO2 N NH3 N Kjeldahl Nitrogen Organic Nitrogen NH3 N Organic Nitrogen Kjeldahl Nitrogen NH3 N The above nitrogen relationships are checked to ensure proper calculations have been performed Trace Organic Contaminants TOX Volatile Organic Halogens Non volatile Organic Halogens Volatile Organic Halogens Polar Non polar Volatile Organic Halogens Non volatile Organic Halogens Polar Non polar Non volatile Organic Halogens Non polar Volatile Organic Halogens are measured from EPA Methods 502 2 601 8010 524 624 8240 or 8260 analysis Non polar Non volatile Organic Halogens are measured from EPA Method 525 625 or 8270 analysis From the above relationships the following is performed TOX Non polar Volatile Non volatile Organic Halides Revision 4 0 Q10 Page 5 of 6 Microbilogy Total Coliform Fecal Coliform Fecal Streptococcus Enterococcus Organics 3 6 Pull up batch in Data Entry Rev
26. analytes Table 1 ANALYTE CAS MCL ppb Aluminum 7429 90 5 1000 Antimony 7440 36 0 6 Arsenic 7440 38 2 50 Barium 7440 39 3 1000 Beryllium 7440 41 7 4 Boron 7440 42 8 Cadmium 7440 43 9 5 Calcium 7440 70 2 Chromium 7440 47 3 50 Cobalt 7440 48 4 Copper 7440 50 8 1000 Iron 7439 89 6 300 Lead 7439 92 1 15 Lithium 7439 93 2 Magnesium 7439 95 4 B Manganese 7439 96 5 50 Mercury 7439 97 6 2 Molybdenum 7439 98 7 Nickel 7440 02 0 100 Potassium 7440 09 7 Selenium 7782 49 2 50 Silica a 7631 86 9 Silver 7440 22 4 100 Sodium 7440 23 5 Strontium 7440 24 6 Thallium 7440 28 0 2 Tin 7440 31 5 Titanium 7440 32 6 Vanadium 7440 62 2 Zinc 7440 66 6 5000 Note Analytes in parenthesis are not certified by NELAP ELAP Certified Revision 4 1 M07 200 7 Page 2 of 21 1 1 1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 INSTRUMENTATION Perkin Elmer Optima 5300DV For reference where this method is approved for use in compliance monitoring programs e g Clean Water Act NPDES or Safe Drinking Water Act SDWA consult both the appropriate sections of the Code of Federal Regulation 40 CFR Part 136 Table 1B for NPDES and Part 141 141 23 for drinking water and the latest Federal Register announcements ICP AES can be used to determine dissolved analytes in aqueous samples after suitable filtration and acid preservation To reduce potential interferences dissolved solids should
27. consult both the appropriate sections of the Code of Federal Regulation 40 CFR Part 136 Table 1B for NPDES and Part 141 Section 141 23 for drinking water and the latest Federal Register announcements Dissolved elements are determined after suitable filtration through 0 45 micron filter and acid preservation In order to reduce potential interferences dissolved solids should not exceed 0 296 w v Sect 4 1 4 Samples may be analyzed directly by pneumatic nebulization without acid digestion if the samples have been properly preserved with acid and have turbidity of 1 NTU at the time of analysis This total recoverable determination procedure is referred to as direct analysis For the determination of total recoverable analytes in aqueous samples a digestion extraction is required prior to analysis when the elements are not in solution e g aqueous samples that may contain particulate and suspended solids Aqueous samples containing suspended or particulate material gt 196 w v are diluted and digested by EPA 3015 The total recoverable sample digestion procedure given in this method is not suitable for the determination of volatile organo mercury compounds However for direct analysis of drinking water turbidity 1 NTU the combined concentration of inorganic and organo mercury in solution can be determined by direct analysis pneumatic nebulization provided gold is added to both samples and standards alike to eliminat
28. possibility of a memory effect and examines the analyte concentration in the previous sample to identify if this was high If memory interference is suspected the sample is reanalyzed after a long rinse period 4 1 6 Environmental interferences see section 6 3 5 SAFETY 5 1 The toxicity or carcinogenicity of reagents used in this method have not been fully established Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonable achievable A reference file of material data handling sheets is available to all personnel involved in the chemical analysis Specifically concentrated nitric and hydrochloric acids present various hazards and are moderately toxic and extremely irritating to skin and mucus membranes Use these reagents in a fume hood whenever possible and if eye or skin contact occurs flush with large volumes of water Always wear safety glasses or a shield for eye protection protective clothing and observe proper mixing when working with these reagents Revision 3 0 M12 200 8 Page 6 of 26 5 2 The acidification of samples containing reactive materials may result in the release of toxic gases such as cyanides or sulfides Acidification of samples should be done in a fume hood 5 3 Analytical plasma sources emit radio frequency radiation in addition to intense UV radiation Suitable precautions should be taken to protect personnel from such hazards
29. swr oouopguo 2566 Es 9 TW O T TW 01 NoLLaTIq d qaas 53901 NIHM SLINSAY 3ALLISOd AO SNOILVNISWOD SQODIVA 3104 SLIAT ADNAGIANOD 2566 XAGN NAIN AI ICC6 318v Revision 5 0 I05 BOI D Page 1 of 8 BIOCHEMICAL OXYGEN DEMAND 5 DAY TEST Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE Standard Methods 5210 B Date Effective 02 01 06 Scope and Application This method is used to determine the relative oxygen requirements of wastewaters This method may also be used for other matrices if both client and regulator agree to this variation Reporting limits The reporting limit for this method is 5 0 mg L Working Range Reporting limit 5 mg L The upper end of the working range is dependent upon the dilutions used Summary of Method The method consists of placing a sample in a full airtight bottle and incubating the bottle under specified conditions for a specific time Dissolved oxygen is measured initially and after incubation The BOD is computed from the difference between the initial and final dissolved oxygen Environmental Relevence The biochemical oxygen demand determination has its widest application in measuring waste loadings to treatment plants and in evaluating BOD removal efficiency of such treatment systems Sample Collection Preservation and Holding Times 6 1 The sample for BOD is collected with a minimum of headspace and re
30. the beaker cover with a watch glass move beaker to the center and continue to digest with rolling fumes about 2 minutes If yellow fumes are present after watch glass is put on the beaker remove the watch glass until yellow fumes are Revision 5 0 TP Page 7 of10 will fill with decrease Drag the rim of accumulating Do not ntire digest on volume bud 142 gone and cover again The beaker fumes and then the fumes will the bottom of the watch glass along the beaker if moisture is allow the beaker to go dry The takes about 10 15 minutes depending and organic content of the sample Let cool Rinse watch glass into the beaker and rinse down sides of beaker with water from the nanopure squirt bottle 8 P 10 10 qs 10 Transfer for sample with each beaker Add 2 drops of phenolphthalein to Neutralize with 6N Sodium Hydroxide by adding one drop at a time using a plastic dropper until it turns pink 1 10 Transfer sample to 10ml graduated cylinder Dilute to 10ml with Nanopure water the sample back to the beaker Check turbidity at this time Redigest less volume if turbid 10 2 Colorimetric Reading 10 2 1 Add 1 6ml P reagent swirl and then allow to stand for minimum of 10 minutes maximum of 30 minutes 10 2 2 Set Spectrophotometer wavelength to 880 nm 10 2 3 Set zero with digested blank 10
31. 0 REFERENCES 14 1 EPA 8081B Methods for the Chemical Analysis of Waters and Wastes 14 2 SW 846 Prop Update IV January 1998 Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 12 12 05 Revision 4 0 Q10 Page 1 of 6 Edward S Babcock Standard Operating Procedure Data Review and Validation Effective Date __05 01 06 1 0 Analyst Review 1 1 The analysts review raw data for the following 1 1 1 Results are calculated correctly Final results on the data page must be calculated not copied from Element 1 1 2 Batch QC meets acceptance criteria 1 1 3 Dilution or concentration factors were correctly applied and chosen appropriately 1 1 4 Proper units were used 1 1 5 Results are reported accurately 1 1 6 Additional reporting requirements were met 1 e QC report notes special requirements 1 2 Once the analyst feels the data is acceptable he she enters the data into Element and reviews the entered data for the following 1 2 1 Raw and final results on the instrument report forms match the data in Element Dilution factors and initial final sample volumes are correct MRL initials of the chemist date and time are correct All red data in Element is corrected or properly qualified pai QU P 1 3 The analyst fills out the Peer Review Checklist using the following directions 1 3 1 Fill out the Checklist completely If a check space is not applica
32. 10 minutes for col development lter Place into the data es LOr Zero the spectrophotometer to the reagent blank Read samples on UV Vis Spectrometer at Record the answer in absorbance units 8 0 Calibration and Calculation 543 nm 8 1 Three calibration standards are required by the method In general calibration standards are prepared at six concentrations including a calibration blank A calibration curve is analyzed on a yearly basis covering the referenced concentration range 8 8 An acceptabl curve 8 4 Results are calculated from the regression equation 2 le curve yields an 0 99 or better 3 A regression equation is generated from the Revision 5 0 I22 NO2 Page 5 of 6 8 5 Enter the raw concentration into the LIMS Ensure that the proper initial volume is entered on the bench sheet 8 6 Immediately following calibration a 0 1 mg L ICV is analyzed using the LCS source to verify the curve Results must be within 90 110 of the expected value or a new curve may be necessary 8 7 Continuing Calibration Verification Checks The calibration is verified on a daily basis by analysis of the Lab Control at the beginning of the day s batch and the Midpoint Check at the end of the day s batch See acceptance criteria below 8 8 Results greater than the highest calibrator must not be reported Dilute result into the calibration range
33. 14 1 Refer to in house quality control performance records 15 0 Corrective Action For Out of Control Or Unacceptable Data 15 1 If any of the above QC samples do not meet acceptance criteria the analyst must take measures to correct the problem 15 1 1 The analyst examines the results of other controls performed that day 15 1 2 The analyst examines sample results either for historical trends or for none detects 15 1 3 If the above investigation indicates that the batch is still valid and the out of control QC appears to be an anomaly results are reported 15 1 4 If it is unclear whether sample results can be verified any affected samples must either be resampled or results must be reported with a note qualifying the data 15 1 5 Out of control QC is noted on the QC data page along with the corrective action taken A QC follow up form is filled out in the computer and added behind the QC data page 16 0 Pollution Prevention and Waste Management 16 1 positive samples and QC are autoclaved prior to disposal 16 2 See also SOP S07 Pollution Prevention Revision 6 0 B02 MTF Page 8 of 9 References Standard Methods for the Examination of Water and Wastewater APHA AWWA WPCF 18th edition 9221 B C E Note All italicized items except bacteria names are an indication of a variation from the method Approved by Date TABLE 9221 MPN INDEX AND 95 CONFIDENCE LIMITS FOR VARIOUS COMBINATIONS OF POSITIVE AND NEGATIVE
34. 15 of the expected value If average criteria is used all reportable results for target analytes must be qualified if that analyte was outside 15 criteria See Q06 for additional details 9 4 2 Atleast 85 of all target analytes in each CCV must be within 15 of the expected value If this is not achieved samples must be reanalyzed or qualified See Q06 for details 9 5 A standard at the reporting limit is analyzed at the end of the run This is used to evaluate instrument sensitivity should calibration checks show a low bias This standard should have a signal greater then the method blank 10 0 QUALITY CONTROL Note See also ESB SOP 01 for general QC requirements 10 1 Minimum quality control QC requirements are initial demonstration of laboratory capability determination of surrogate compound recoveries Monitoring internal standard peak area or height in each sample and blank analysis of laboratory reagent blanks laboratory fortified samples laboratory fortified blanks and QC samples 10 2 Laboratory Reagent Blanks Before processing any samples the analyst must demonstrate that all glassware and reagent interferences are under control Each time a set of samples is extracted or reagents are changed a LRB must be analyzed per matrix type If within the retention time window of any analyte of interest the LRB produces a peak that would prevent the determination of that analyte determine the source of contamination and eliminate
35. 2 28 days total dissolved solids TDS 1060 B 500 Plastic 4 7d total hardness 1060 B 60 Plastic 4 C HNO 6 mo dissolved organic carbon DOC 1060 B 40 Glass Filter 4 C H2SO 28d total organic carbon TOC 1060 B 40 Glass 4 H SO4 28d dissolved manganese 1060 B 60 Plastic Filter HNO to pH lt 2 6 months dissolved iron Fediss 1060 B 60 Plastic Filter HNO to pH 2 6 months total iron Feria 1060 B 60 Plastic to pH 2 6 months ET 4 C field Filter H250 total organic nitrogen 1060 B 125 Plastic to pH 2 lab 28 days total inorganic nitrogen TIN 1060 B 125 Plastic 4 C lab Filter H2SO4 to 28 days pH 2 lab organic phosphorus 1060 B 125 Plastic 4 C 28 days Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 30 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS Once sample containers are filled they are assigned a unique identification label number Individual sample labels consist of a site number depth and the sampling date The samples are stored on ice until transported to the laboratory for analysis San Jacinto storm event samples prepared for laboratory analysis will be labeled and recorded in a San Jacinto Storm Event Field Data Form at the time of collection Entries will include the date names of sampling personnel weather conditions site number time of sampling depth whether a Hydr
36. 2 4 Read ABS of standard and record Revision 5 0 T42 TP Page 8 of10 10 2 5 Record absorbance of samples If result is over 1 mg L dilute and re digest a new aliquot of sample 11 0 Calibration TE SAT A six point curve plus the zero point required by the method is analyzed on a yearly basis covering the referenced concentration range 2 An acceptable curve yields an r 0 99 or better Ho A regression equation is generated from the curve 24 Results are calculated from the regression equation Immediately following calibration a 0 5 mg L ICV is analyzed using the LCS source to verify the curve Results must be within 90 110 of the expected value or a new curve may be necessary 11 6 Continuing Calibration Verification Checks The calibration is verified on a daily basis by analysis of the 0 25 mg L Calibration Check analyzed at the end of the day s batch Recovery of these checks must be within 85 115 of expected value 12 0 Quality Control Note See also ESB SOP 001 for general QC requirements T2 Laboratory Control Conc 0 5ppm TAE ren A LCS is analyzed once per batch or for every 20 samples whichever is greater and reported per matrix type qr The results must be within the acceptance range of 80 120 or the analysis is considered to be out of control The Revision 5 0 I42 Page 9 of10 problem must be c
37. 2 5 5 times the estimated MDL into Nanopure water for aqueous studies and onto sand for nonaqueous minimum of seven replicates is analyzed See QA Manual for calculation Results must within 2 2 times the reporting limit Past studies were performed at midrange Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 4096 for Organic analyses Performance Evaluation Studies are performed twice a year ASSESSING METHOD PERFORMANCE LABORATORY FORTIFIED SAMPLE MATRIX 8 8 1 The laboratory adds a known concentration to a minimum of 5 of the routine samples per matrix type or one sample concentration per set whichever is greater 8 8 2 Acceptance ranges are generated from historical data See LIMS for most current limits 8 8 3 A MS is acceptable if 80 or more of the analytes fall within the laboratory prescribed acceptance criteria 8 8 4 If the recovery of any such analyte falls outside the designated range and the laboratory performance for that analyte is shown to be in control the recovery problem encountered with the dosed sample is judged to be matrix related not system related QC For Florisil Clean Ups 8 9 1 Perform a florisil method
38. 20D set at 880nm 8 0 Glassware Preparation tered Blank and tered Blank Genesys 10uv and 8 1 All glassware is acid washed in 1 1 HCl immediately after use followed by thorough rinsing with three portions of D I wa still appears dirty further s D I rinse 9 0 Phosphate Reagents 9 1 Reagent water Nanopure tep ter If glassware s are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final 9 2 P Reagent Let all reagents reach room temperature before mixing Mix in the order given If turbidity forms in the combined reagent shake and let stand for a few minutes until turbidity disappears before proceeding The for 4 hours at room temperature the reagent can be kept and used for 3 days assuming all QC samples meet the proper acceptance criteria Place reagent immediately back in the refrigerator after use to preserve its integrity When fresh the reagent should be light yellow If reagent is stable If refrigerated Revision 4 5 0 OP Page 4 of 9 the reagent turns gold it reagent in glass 9 2 9 2212 Prepare two beakers I27 is too old Store as follows 9 2 1 1 Beaker 1 0 53 g Ascorbic acid and 30mL nanopure water Make fresh before each batch analysis 9 2 1 2 Beaker 2 50mL 5N Ho5SO4 5mL Potassium Anti
39. 21 2 2 2 3 An aliquot of a well mixed homogeneous aqueous sample is accurately measured for sample processing For total recoverable analysis of an aqueous sample containing undissolved material analytes are first solubilized by microwave digestion with nitric and hydrochloric acid After cooling the sample is decanted or filtered prior to analysis For the determination of dissolved analytes in a filtered aqueous sample aliquot or for the direct analysis total recoverable determination of analytes in drinking water where sample turbidity is NTU the sample is made ready for analysis by the appropriate addition of nitric and hydrochloric acid and then diluted to predetermined volume and mixed before analysis The method describes the multi element determination of trace elements by ICP MS 1 3 Sample material in solution is introduced by pneumatic nebulization into a radio frequency plasma where energy transfer processes cause desolvation atomization and ionization The ions are extracted from the plasma through a differentially pumped vacuum interface and separated on the basis of their mass to charge ratio by a quadrupole mass spectrometer having a minimum resolution capability of 1 amu peak width at 5 peak height Our laboratory uses the Perkin Elmer Elan 6000 and 9000 for this analysis The ions transmitted through the quadrupole are detected by a electron multiplier or Faraday detector and the ion information processed by
40. 3 2 above 6 0 Metals 6 1 To preserve for trace metals acidify the sample with 1 1 nitric acid to a pH of less than 2 units Place a N on the Work Order Printout and sample 6 2 If the sample is reactive upon addition of acid the splitter lets the reaction finish and then rechecks the pH If the pH is not 2 place a NOT 2 on the lid of the sample next to the N and on the Work Order Printout Note on sample and Work Order that sample is reactive 6 3 If metals require filtration see section 3 7 1 for instructions 7 0 Chemical Oxygen Demand COD 7 1 Collect the samples in glass bottles if possible Use of plastic containers is permissible if it is known that no organic contaminants are present in the containers 7 2 Samples should be analyzed as soon as possible or preserved with approximately 3 to 4 drops 1 1 sulfuric acid per snap cap of sample to a pH 2 and maintained at 4 C until analysis Analysis must take place within 28 days Samples kept in plastic bottles or snap caps in the refrigerator on the sulfuric preserved cart Place a COD on the Work Order Printout and a S on the sample 8 0 Kjeldahl Nitrogen TKN Ammonium NH4 Total Phosphate TP 8 1 Preserve samples with approximately 2ml of 1 1 sulfuric acid per quart of sample to pH 2 After a homogeneous subsample has been separated into a quart plastic bottle add H2SO Mix the bottle test the pH by pouring a portion of the Revision 3 0 06 Page 5 o
41. 4 3 The batch is reanalyzed or re extracted with acceptable QC Contact the client to determine if re extraction past holding time is an acceptable option 1 5 4 4 If management deems the batch reportable results are reported with the proper qualifiers 1 5 4 4 1 All samples with results at or above the reporting limit are flagged with a qualifier on the sample analytes signifying a low or high bias NLOlo or NLOhi 1 5 4 4 2 Samples that are ND 1 5 4 4 2 1 Ifthe LCS is bias high a qualifier is not necessary as long as all analytes in the sample are ND 1 5 4 4 2 2 If the LCS is bias low the RL check must be acceptable for that analyte and sample surrogate compounds must be acceptable otherwise a qualifier must be placed on the sample analytes NLOlo Marginal exceedances must be random If the same analyte exceeds the LCS control limit repeatedly 2 batches out of the most recent 3 batches it is an indication of a systemic problem The source of the Revision 7 0 006 Page 3 of 11 error must be located and corrective action taken To ensure random behavior marginal exceedance allowance to the LCS is monitored on the peer review sheet 2 0 Method Blank 2 1 2 2 2 3 24 25 2 6 2 7 When a method blank is out of the laboratory acceptance criteria stated in the SOP the batch validity is called into question Examine the calibration zero point and or baseline for contamination Examine scale tare weights Examin
42. 7 3 7 3 Calculate the standard deviation SD and the RSD of the calibration factors for each analyte as 4 CFi CE SD RSD x 100 CF A linear curve must have a correlation coefficient r 0 99 A nonlinear curve must have a coefficient of determination gt 0 99 Alternatively if the ratio of response to concentration calibration factor is a constant over the working range 20 RSD or less linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve Revision 4 0 Page 9 of 16 7 3 9 7 3 10 O54 8081 If due to the long list of compounds every analyte cannot meet the above criteria a calibration can be accepted if the mean of the RSD values of all analytes in the calibration is 20 If the mean criteria is used instead of individual RSD or coefficients reportable results must be qualified for analytes outside 20 criteria calibrations are verified by the analysis of an ICV standard usually the LCS made from a noncalibration source The calibration factor for each single component analyte should not exceed a 15 percent difference from the mean calibration factor calculated for the initial calibration If this criterion is exceeded for any analyte calculate the average percent difference across all analytes If the average of the responses is within the 15 limit then the calibration has been verified If average criteria
43. 8081 3L f m Unpreserved 7 8081 3L p Unpreserved 7 b BHC OC EPA 8081 3L 1 ju Unpreserved 7 g BHC Lindane OC EPA 8081 3L ms Unpreserved 7 d BHC OC EPA 8081 3L 1 poo Unpreserved 7 Chlordane OC EPA 8081 3L IE ed Unpreserved 7 4 4 DDD OC EPA 8081 3L 1 Pd Unpreserved 7 4 4 DDE OC EPA 8081 3L 1 pd Unpreserved 7 4 4 DDT OC EPA 8081 3L 1 Fo Unpreserved 7 Dieldrin OC EPA 8081 3L po Unpreserved 7 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Endosulfan OC Endosulfan Il OC Endosulfan sulfate OC Endrin OC Endrin aldehyde OC Heptachlor OC Heptachlor epoxide OC Hexachlorobenzene OC Hexachlorocyclopentadiene OC Methoxychlor OC Toxaphene OC organophosphate OP pesticides Aspon OP Azinphos methyl OP Azinphos ethyl OP Bolstar Sulprofos OP Carbophenothion OP Chlorfenvinphos OP Chlorpyrifos OP Chlorpyrifos methyl OP Coumaphos OP Crotoxyphos OP Demeton O OP Demeton S OP Diazinon OP Dichlorofenthion OP Dichlorvos DDVP OP Dicrotophos OP Dimethoate OP Dioxathion OP Disulfoton OP EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081 EPA 8081
44. 9 6 5LCS into kept if com Nanopure water Six point curve fresh each time Control 0 5ppm In desiccator termediate 500ppm of Nanopure This for up to 12 m problem 9 6 6Workin Intermediate Filter and analyze as specified in sections 12 4 9 6 Intermediate standard into 1L of to create a Solutions are made ion source of 2 4 a 105 C oven and stored Dilute 2 197g KH2PO standard may be onths or replaced sooner parison with QC samples indicate a 10uL of LCS g LCS 0 5ppm Spike into 10mL of 12 6 7Calibration Check 0 25ppm Intermediate into 10mL of Nanopure water Spike 5uL of LCS Nanopure water Analyze as specified in sections 12 4 12 6 10 0 Note See also ESB TOLL A DES xs 20 samples whichever e result Th analysis must be Quality Control SOP Q01 for general QC requirements analyzed once per bai tch or 1 for every is greater and report is considered to be out of control 10 2 10 52 10mL corrected befor the analysis Matrix Spike and Matrix Spike Spike 10uL of LCS Intermediate ted per matrix type must be within acceptance ranges of 90 110 or the The problem can continue Duplicate 0 5ppm into of sample Analyze as specified in sections 12 4 Revision 5 0 I27 OP Page 6 of 9 10 2 2 An MS MSD is
45. All field instruments will be inspected and calibrated prior to visiting the field Calibration results will be recorded in the field instrument calibration log All laboratory equipment used to provide numerical data will be calibrated to the accuracy requirements for its use prior to periodically during and at the end of sample analysis Facilities and instrumentation used in conjunction with these studies e g balances will be regularly checked and confirmed to be operating within manufacturers specifications Devices not meeting specifications will be returned to the manufacturer for servicing 7 Inspection of Supplies and Consumables Sample containers will be washed and inspected before use All sampling containers and laboratory glassware will washed using the appropriate detergents followed by rinsing with tap water acid wash where appropriate and final rinses with distilled water followed by deionized water Chemical calibrations and standardizations are made using standards prepared from materials of known purity reagent grade or better using accepted analytical techniques Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 7 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE References 1998 Standard Methods for the Examination of Water and Wastewater 20 Edition American Public Health Association Washington DC Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon
46. Ana Regional Water Quality Control Board Date Riverside County Flood Control amp Water Conservation District Date MWH Date Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 3 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A2 TABLE OF CONTENTS Page SECTION PROJECT MANAGEMENT ELEMENTS 1 Al APPROVAL SIGNATURES 55 2 21 TABEE OE CONTENTS inse eren edite pito cot 3 A34 DSI RBU TON ES oo eR ast nanos roe a ee eot recep eter tes ales ne tou Er eov Pete E Ren 5 A4 PROJECT TASK ORGANIZATION AND RESPONSIBILITIES ccce 6 AS PROBLEM DEFINITION AND 11 A6 PROJECT TASK DESCRIPTION 13 A7 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT 19 A8 SPECIALIZED TRAINING REQUIREMENTS eeeeseeseeeeeeeeeene enne 21 9 DOCUMENTATION AND RECORDS 22 SECTION MEASUREMENT DATA ACQUISITION 24 Bl SAMPLING PROCESS DESIGN cene nnne 24 B2 SAMPLING METHODS REQUIREMENTS sseeeeseseeeeeeeeeeeehe nenne 25 SAMPLE HANDLING AND CUSTODY REQUIREMENTS eese 30 B4 ANALYTICAL METHODS REQUIREMENTS
47. Analytes appearing in the calibration standards that are not part of the LIMS reporting lists will be noted with parentheses as nontarget analytes These analytes are not evaluated for calibration acceptance since their results are not reported to clients If a special request is made to report these analytes then calibration acceptance will be evaluated 5 6 2 Ifall of the individual target analytes do not meet CCV acceptance criteria a run may still be accepted as long as 8596 or more of the target analytes in an individual CCV fall within method acceptance criteria Target analytes outside method acceptance criteria must be qualified See section 4 5 4 2 1 and 4 5 4 2 2 for qualifier details 6 0 Surrogate Recovery 6 1 Surrogate recovery is acceptable if compound response falls within laboratory prescribed acceptance limits If samples are spiked with multiple surrogate compounds the following acceptance criteria applies of surr compounds of surr compounds in spike allowed outside acceptance limits 1 2 0 3 4 p 5 or more see specific SOP Examine the entire run If the same surrogate compound is out in more than 20 of the samples perform maintenance prior to analyzing the next batch 6 2 If there is reasonable evidence documented with the raw data to suspect that 6 3 6 4 the spiking solution was made incorrectly Evaluate recovery based on the new spiking level and report results without a qualifier If
48. Any drinking water sample producing turbid cultures heavy growth which inhibit an accurate gas production reading is automatically transferred to confirming media positives on confirming media are reported as such all negatives are reported as invalid and a resample is requested In either case a note indicating the presence of turbidity is placed on the bottom of the lab sheet 11 2 Confirmed Phase Each broth tube which shows CO formation inside the Durham tube is transferred to a brilliant green bile tube Insert a transfer loop into the positive tube stir and then place loop into the brilliant green bile tube These tubes are incubated at 35 C 0 5 C for a total of 48 3 hours If gas formation is present in their Durham tubes when examined after 24 2 or 48 3 hours the sample is considered positive for total coliform bacteria The positive broth tubes are also transferred to E C media wastewaters or E C MUG drinking waters The tubes of media also contain Durham tubes After the sample has been transferred to the tubes the tubes are incubated at 44 5 C 0 2 C for only 24 2 hours in the fecal water bath Tubes are placed in the water bath within 30 minutes of inoculation If CO formation is observed in the EC tube after the incubation period the sample is considered positive for fecal coliform bacteria EC tubes that are so turbid that the Durham tube is difficult to see are considered positive if there is
49. Field Log Form 3 Example Chain of Custody Form APPENDICES A E S Babcock and Sons Inc Laboratory Standard Operation Procedures B University of California Riverside Dr Michael Anderson Laboratory Standard Operation Procedures E S Babcock and Sons Inc Laboratory Analytical Information 2n Sampling Plan E S Babcock and Sons Inc Laboratory QA Manual Instructions for the Oakton Waterproof pHTestr 2 Instructions for the Oakton TDSTestr 20 Qmm Lake Elsinore Canyon Lake TMDL Compliance Program San Jacinto River Watershed Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 5 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A3 DISTRIBUTION LIST Title Name Affiliation Tel No No of copies TASK FORCE Administrator Mark Norton 951 354 4221 1 Lake Elsinore amp San Jacinto Watersheds Authority San Jacinto Watershed Pat Boldt 951 808 8531 1 Component of the Santa Ana San Jacinto River Watershed Integrated Watershed Plan Council San Jacinto River Alex Gann 951 955 1180 1 Improvement and Protection Riverside County Program TMDL Program Manager Hope Smythe 951 782 4493 1 Santa Ana Regional Water Quality Control Board Quality Assurance Program Pavlova Vitale 951 782 4920 1 Manager Santa Ana Regional Water Quality Control Board Grant Manager SJRIPP David Woelfel 951 782 7960 1 Santa Ana Regional Water Quality Control Board TASK FORCE Monitoring Rick Whetsel 951 354 4222 1 Program
50. ID 0 25 um phase thickness 4 1 5 Confirmatory Detector Electron Capture Detector 4 1 6 Confirmatory Column SPB 608 30m x 0 25mm ID 0 25 um thickness 4 1 7 Column Conditions 4 1 7 1 Injector Temp 220 C 4 1 7 2 Detector Temp 320 C 4 1 7 3 Initial Temp 120 C 4 1 7 4 Initial Hold 4 min 4 1 7 5 Rate 5 C min 4 1 7 6 Final Temp 280 C 4 1 7 7 Final Hold Time 4 min 4 1 7 8 He Carrier head pressure set to 180kPa 4 1 7 9 Make up set to 60 mL min All results are reported from the primary column and confirmed using the secondary column unless analytical conditions and quality control samples indicate that the secondary column results are more accurate See ESB SOP Q20 for details If in any case the secondary column is used for quantification the analyst must document reasoning for doing so 5 0 REAGENTS 5 1 5 2 5 3 54 Reagent grade or pesticide grade chemicals are used in all tests Other grades may be used provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination Solvents used in the extraction and cleanup procedures and for standards include n hexane methylene chloride MtBE and acetone Organic free reagent water Nanopure STOCK STANDARD SOLUTIONS Stock standards are purchased from a certified manufacturer Pesticides are in a 9096 Hexane 1096 Acetone mix Solutions are stored in sealed vials pro
51. Lake Elsinore Canyon Lake and San Jacinto River Watershed Nutrient TMDL Monitoring The Lake Elsinore and Canyon Lake Nutrient TMDL Task Force is a stakeholder based organization formed to address the overlapping obligations of stakeholders to implement the Lake Elsinore and Canyon Lake Nutrient TMDLs as mandated in Regional Board Resolution No R8 2004 0037 The TASK FORCE is administered by the Lake Elsinore amp San Jacinto Watersheds Authority LESJWA and includes Riverside County and the SJRWC as TASK FORCE members The TASK FORCE has a Technical Advisory Committee TAC which advises on all tasks performed by the TASK FORCE and will oversee the sample collection efforts and the initiation and maintenance of agreements with contracting laboratories for the Lake Elsinore Canyon Lake and San Jacinto River Watershed Monitoring programs TASK FORCE PROGRAMS The organizational structure of the TASK FORCE is diagramed in Figure 1 Mr Mark Norton is the TASK FORCE Administrator He will be responsible for overseeing all aspects of the program including the naming of the Monitoring Program Manager Mr Rick Whetsel is the Monitoring Program Manager will be responsible for the coordination of the three main components of the Lake Elsinore and Canyon Lake Nutrient TMDL monitoring program including 1 The San Jacinto Watershed nutrient monitoring program 2 The Lake Elsinore nutrient monitoring program and 3 The Canyon Lake nutrie
52. Lake Nutrient TMDL TASK FORCE APPENDIX C E S BABCOCK AND SONS INC LABORATORY ANALYTICAL INFORMATION Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX D LAKE ELSINORE CANYON LAKE TMDL COMPLIANCE PROGRAM SAN JACINTO RIVER WATERSHED SAMPLING PLAN Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX E E S BABCOCK AND SONS INC LABORATORY QA MANUAL Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX F INSTRUCTIONS FOR THE OAKTON WATERPROOF PHTESTR 2 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX G INSTRUCTIONS FOR THE OAKTON TDSTESTR 20
53. Manager Lake Elsinore amp San Jacinto Watersheds Authority San Jacinto Watershed Steve Clark 951 955 1346 1 Quality Assurance Manager Riverside County Flood Control amp Water Conservation District Lake Elsinore Sarah Garber 626 568 6910 1 Quality Assurance Manager MWH Canyon Lake Dr Michael Anderson 951 787 3757 1 Monitoring Program Manager University of Riverside Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 6 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A4 PROJECT TASK ORGANIZATION AND RESPONSIBILITIES Involved Parties and Roles This QAPP serves three interrelated projects e The Lake Elsinore Canyon Lake and San Jacinto River Watershed nutrient TMDL Monitoring Programs conducted by the Lake Elsinore and Canyon Lake Nutrient TMDL Task Force TASK FORCE e The San Jacinto River Improvement and Protection Program SJRIPP a Proposition 13 Watershed Protection Grant project administered by Riverside County e The San Jacinto Watershed Component of the Santa Ana Integrated Watershed Plan a Proposition 50 Chapter 8 Planning Grant project administered by the San Jacinto River Watershed Council SJRWC These three projects interrelate and to varying extents overlap For example although the lead administrating agency is different for each project all three administrators are at least stakeholders if not partners in each other s project A more detailed summary of each project follows
54. Method interferences may be caused by contaminants in the reagent water reagents glassware and other sample processing apparatus that lead to discrete artifacts or elevated baseline in ion chromatograms 4 4 Samples that contain particles larger than 0 45 microns and reagent solutions that contain particles larger than 0 20 microns require filtration to prevent damage to instrument columns and flow systems Caution filtration may remove perchlorate 4 5 Any anion that is not retained by the column or only slightly retained will elute in the area of fluoride and interfere Known coelution is caused by carbonate and other small organic anions At concentrations of fluoride above 1 5 mg L this interference may not be significant however it is the responsibility of the user to generate precision and accuracy information in each sample matrix 4 6 The acetate anion elutes early during the chromatographic run The retention times of the anions also seem to differ when large amounts of acetate are present Therefore this method is not recommended for leachates of solid samples when acetic acid is used for pH adjustment 4 7 The quantitation of unretained peaks should be avoided such as low molecular weight organic acids formate acetate propionate etc which are conductive and coelute with or near fluoride and would bias the fluoride quantitation in some drinking and most waste waters 5 0 Safety Revision 7 0 119 Anions Page 4 of 15
55. Program Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 23 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE sample collection records sample transport records chain of custody and field analyses forms and all records submitted by contract laboratories associated with the LE nutrient monitoring program The CL Quality Assurance Manager will maintain all CL Nutrient Monitoring Program sample collection records sample transport records chain of custody and field analyses forms and all records submitted by contract laboratories associated with the CL nutrient monitoring program Each laboratory contracted by the TASK FORCE will appoint a Quality Assurance Manager to maintain the laboratory s records The TASK FORCE Monitoring Program Manager will oversee the actions of these persons and will maintain the Lake Elsinore and Canyon Lake nutrient TMDL database which will include all sample analyses results that have passed all QA processes as defined in this Plan The Task Force Monitoring Program Manager will also arbitrate any issues relative to records retention and any decisions to discard records The SJRIPP Program Administrator shall maintain copies of all reports and have access to all monitoring program sample collection records sample transport records chain of custody and field analysis forms and all records submitted by contract laboratories associated with the SJRIPP activities As per the grant agreement th
56. Proposition 13 Watershed Protection Program Grant to address a significant volume of illegal dumping activities which has degraded water quality habitat for sensitive species and has blighted the watershed The County proposes to address these issues through a comprehensive program that would address point and non point pollution along the San Jacinto River including woody debris that may be providing nutrients to the lakes This includes sponsoring trash clean up days fencing areas at risk of illegal dumping and acquiring properties along the San Jacinto River to restrict access reduce illegal dumping protect riparian habitat and provide buffers from other land uses San Jacinto Watershed Component of the Santa Ana Integrated Watershed Plan The SJRWC was awarded a Proposition 50 Chapter 8 Planning Grant to develop the SJR Component The SJR Component is an Integrated Regional Water Management Plan for the San Jacinto River Watershed Funding for this plan will be used to conduct watershed monitoring for the purpose of identifying viable watershed projects Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 13 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A6 DESCRIPTION The TASK FORCE TMDL sampling program includes the following tasks Implementation of a Nutrient TMDL monitoring program in the San Jacinto Watershed A watershed wide monitoring program will determine compliance with interim and
57. RESULTS WHEN TEN 10 ML PORTIONS ARE USED No of Tubes 95 Confidence Limits Giving Positive MPN Approximate Reaction Out of Index MH 10 of 10 mL Each 100 mL Lower Upper 0 Lil 0 3 0 1 LI 0 03 5 9 2 22 0 26 8 1 3 3 6 0 69 10 6 4 d 13 13 4 5 6 9 2 1 16 8 6 9 2 3 1 21 1 7 12 0 4 3 27 1 8 16 1 25 9 36 8 9 23 0 8 1 59 5 10 223 0 13 9 Infinite B02 MTF m 009T S S S 9 9c cre 00 009 009T res gs 0 6 Ic rrr 006c 00 006 E S S 9p OL LI 0 1 0007 007 00 css Sr 0L LI 1 0 OOET 001 00 1 5 6 8t os I 0 0 06 001 Orc 0 08 091 Ose or OL LI 069 01 O87 b S St 0 9 pI OZE 085 001 Occ cis SE 0 9 pI rre 08t 0L 0 1 T p 6c Or FEE 06 os OET 0 t S 6c Or f T 0 t 08 OLI S vc 0 8 0 0 09 09 OFT CCS 6c O S 0 00 Or On FES Sc 0 6 0 7 7 OST 0 08 0 vc 0 6 FEG 082 OP 06 TTS oz L 0 rc orz 0 OL Pes 0c 07 L 1 0 7 0 1 0c Os rcs LI 0I 14 0 0 7 081 0 09 crs 8I 0 9 0 7 1 OST 0c Os 1 1 5 81 07 9 1 1 1 al 0I 0 O 1 S SI OT t 0 1 1 0c OP TOS SI OT L OTI OL 0 1 0 5 OT 4 0 0 1 98 0 6 c 0 0 5 08 9I ve O t t I OT t 0 7 0 LL SI t Lt OL OT 0 1 0 L9 al LC 0 r 0I OT c 1 0 0 9 cl 9c bct g gt 0 0 0 96 0 6 cC 0 ct on IMOT 001 s an soqd jo IMOT 001 SOAIISOg JO TEAL EE EIS NAWN uoneutquio X9pU NAN EX SyumTeouopguo 9596
58. The inductively coupled plasma should only be viewed with proper eye protection from UV emissions 5 4 Itisthe responsibility of the user of this method to comply with relevant disposal and waste regulations For guidance see Sections 15 0 6 EQUIPMENT AND SUPPLIES 6 1 Inductively coupled plasma mass spectrometer 6 1 1 Instrument capable of scanning the mass range 5 250 amu with a minimum resolution capability of 1 amu peak width at 596 peak height Instrument may be fitted with a conventional or extended dynamic range detection system Our laboratory uses the ELAN 6000 and 9000 DRCe with the extended dynamic range detection system NOTE Ifan electron multiplier detector is being used precautions should be taken where necessary to prevent exposure to high ion flux Otherwise changes in instrument response or damage to the multiplier may result 6 1 2 Radio frequency generator compliant with FCC regulations 6 1 3 Argon gas supply High purity grade 99 9996 When analyses are conducted frequently liquid argon is more economical and requires less frequent replacement of tanks than compressed argon in conventional cylinders 6 1 4 A variable speed peristaltic pump is required for solution delivery to the nebulizer Our laboratory uses a Gilson system 6 1 5 Amass flow controller on the nebulizer gas supply is required A water cooled spray chamber is used for reducing some types of interferences e g from polyatomic
59. Then read the transmittance of the reagent blank Record this value on the data page If the transmittance has changed more than 2 or a new lot of vials is started a new reagent blank must be digested and used to zero the spec per manufacturers instructions Hach COD Reaction Model 45600 pg51 Generally the method blank for the week will serve as the reagent blank for the following week unless transmittance varies more than 2 or a new lot of vials is started 8 12 Select Change Mode until absorbance appears Select Measure Blank and read the samples 8 13 Wipe method blank vial 1 off with a damp tissue and dry off making sure vial is clean and free of fingerprints Place vial in the spec with the label facing forward Read the absorbance and remove the blank Read LCS and samples without changing anything Product Variation 9 1 Dissolved COD results are obtained by filtering the sample thru a 0 45 micron filter and then proceeding with the analysis in step 8 4 10 0 Calibration and Calculation Revision 5 0 I07 COD Page 5 of 7 Draft 10 1 Five calibration standards are required by the method In general calibration standards are prepared at seven concentration levels including Zero A new curve is prepared on a yearly basis covering the referenced concentration range 10 2 An acceptable curve yields an r 0 99 or better 10 3 A regression equation is generated from the curve 10 4 Results are calculated using the regre
60. VOS 4 5 Cupric ion may cause low results by catalyzing decomposition of the diazonium salt 4 6 Chlorine converts NO2 and may be the reason for low results 4 7 Suspended material is removed by filtration Color is removed by filtration or by subtracting a background absorbance reading 5 0 Apparatus 5 1 Filtration apparatus or 0 45 micron disk filters 5 2 Spectrophotometer equipped with 1 cm or larger cells for use at 543nm 5 3 Standard laboratory glassware volumetric flasks 100 mL beakers graduated cylinders pipets Note All glassware is cleaned immediately after use by thorough rinsing with three portions of D water If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 6 0 Reagents and Standards 6 1 Reagent water D I water free of nitrite and nitrate is to be used in preparation of all reagents and standards and for sample dilutions 6 2 Color Reagent 6 2 1 To 800 mL of D I add 100 mL 85 phosphoric acid and 10 grams of sulfanilamide 6 2 2 Mix until sulfanilamide is dissolved completely 6 2 3 Add 1 gram N 1 naphthyl ethylenediamine dihydrochloride mix to dissolve 6 2 4 Dilute to 1L with D I water 6 2 5 Solution is stable for about a month when stored in a dark bottle in the refrigerato
61. Wastes EPA 9060 Methods for the Chemical Analysis of Waters and Wastes Standard Methods For the Examination of Water and Wastewater APHA AWWA WPCF 18 Edition 5310B Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 09 20 06 Revision 4 1 53 8141 Page 1 of 16 Standard Operating Procedure Edward S Babcock amp Sons Date Effective 9 27 04 METHOD 8141B TITLE Determination Of Organo Phosphorus Pesticides In Water By Gas Chromatography With A Nitrogen Phosphorus Detector and GCMS Confirmation 1 0 SCOPE and APPLICATION 1 1 This is a gas chromatographic GC method applicable to the determination of organo phosphorus pesticides in groundwater samples sludge and soil samples The following compounds can be determined using this method Range Groundwater samples 4 ug L 50ug L Solid samples 1 mg kg 3 33 mg kg Sludge samples 3 mg kg 10 mg kg Table 1 Analyte CAS ft Aspon 3244 90 4 Atrazine 1912 24 9 Azinphos ethyl 2642 71 9 Azinphos methyl 86 50 0 Bolstar Sulprofos 35400 43 2 Carbophenothion 786 19 6 Chlorfenvinphos 470 90 6 Chlorpyrifos 2921 88 2 Chlorpyrifos methyl 5598 13 0 Coumaphos 56 72 4 Crotoxyphos 7700 17 6 Demeton O 8065 48 3 Demeton S 8065 48 3 Diazinon 333 41 5 Dichlorofenthion 97 17 6 Dichlorvos 62 73 7 Dicrotophos 141 66 2 Dimethoate 60 51 5 Dioxathion 78 34 2 Disulfoton 298 0
62. Wastes are dumped in the High Acid Concentration Waste barrel 18 0 Method Performance 18 1 Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office References Revision 5 0 I27 OP Page 10 of 9 Standard Methods for the Examination of Water and Wastewater AWWA APHA WEF 18 Edition 4500 P E Note 11 italicized items are an indication of a variation from the method Approved by Susan K Thomas Date 08 23 06 Revision 5 0 I29 TDS Page 1 of 8 RESIDUE TOTAL FILTERABLE Total Dissolve Solids Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE Standard Methods 2540C Effective Date 09 22 06 1 0 Scope and Application 1 1 This method is applicable to drinking surface and saline waters domestic and industrial wastes 1 2 This method may also be used for solid samples if both client and regulator agree to this variation See section for details 1 3Environmental Relevance 1 3 1TDS are both inorganic and organic in origin Inorganic sources are minerals such as calcium magnesium and bicarbonate from rocks Organic TDS can come from leaves industrial waste and sewage TDS in a water sample comes from natural sources such as the bedrock and decaying plant material and introduced sources such as waste urban runoff and chemicals left over from water treatment processes A constant
63. a data handling system Interferences relating to the technique Sect 4 are recognized and corrected Such corrections must include compensation for isobaric elemental interferences and interferences from polyatomic ions derived from the plasma gas reagents or sample matrix Instrumental drift as well as suppressions or enhancements of instrument response caused by the sample matrix are corrected by the use of internal standards Environmental Relevance Metals pose a variety of health risks and are monitored for various reasons Some are monitored simply for as aesthetic nuisance while others may cause serious damage to the liver kidney circulatory or nervous systems Metals occur in the environment both naturally and from various manufacturing processes 3 DEFINITIONS 3 See SOP Q15 SOP Definitions 4 INTERFERENCES Revision 3 0 M12 200 8 Page 4 of 26 4 1 Several interference sources may cause inaccuracies in the determination of trace elements by ICP MS These are 4 1 1 Isobaric elemental interferences Are caused by isotopes of different elements which form singly or doubly charged ions of the same nominal mass to charge ratio and which cannot be resolved by the mass spectrometer in use All elements determined by this method have at a minimum one isotope free of isobaric elemental interference Of the analytical isotopes recommended for use with this method Table 4 only molybdenum 98 ruthenium and se
64. a representable sample The sample should be broken up with a sterile transfer loop and then added to 100 mL of sterile dilution water The sample mixture should be allowed to soak for 10 minutes and shaken repeatedly to ensure a homogenous mixture 10 2 2 Depending on the type of sample different serial dilutions may be considered Dry soils are generally inoculated at 1 mL to 0 01 mL Dried sludges are started at 1 mL and diluted to 0 001 mL 10 2 3 The MPN for a solid sample is calculated using the following equation MPN from Chart X X any dilution factor Where A number of grams customer wants the MPN calculation based on usually one gram B Number of grams added to 100 mL of sterile dilution water usually 10 grams 11 0 Daily reading and recording of incubated samples EC MUG 11 1 Presumptive Phase The tubes are incubated at 35 0 5 C 24 2 hours after the sample has been added into the tubes of sterile broth the tubes are removed from the incubator and examined A negative result will show no CO formation inside the Durham tube The negative broth tubes are re incubated for another 24 3 hours After the total 48 3 hours of incubation shows no CO formation in the Durham tubes the test is completed and the sample is considered negative for coliform bacteria The broth tubes which do contain CO bubbles are considered presumptively positive for coliform bacteria and proceed to the confirmed phase
65. aliquot of water is spiked at the level of 2 3 times the MDL The sample is analyzed Analyte response must be greater than method blank response to verify the MDL for each column 11 0 Procedure 11 1 Set up 11 1 1 Prepare Eluant Turn He valve to 5psi Check that the He line is connected to the eluant bottle Set pump rate as per table 1 11 1 2 On peaknet program click on run icon Under file click on load method anion 300 11 1 3 Wait for conductivity and pressure to stabilize 11 2 Standardization and Calibration 11 2 1 Using a clean syringe fill one vial with the Method Blank by filtering Nanopure through a 0 2 um disc filter 11 2 1 1 Place vial in position 1 of autosampler 11 2 1 2 Press START enter 11 2 1 3 Init V 1 enter 11 2 1 4 Rinse 0 enter 11 2 1 5 Last V 1 enter 11 2 2 Using a clean syringe fill one vial with an initial calibration verification standard 11 2 2 1 Place vial in position 2 of autosampler 11 2 2 2 Press START enter 11 2 2 3 Init V 1 enter 11 2 2 4 Rinse 0 enter 11 2 2 5 Last V 2 enter 11 2 3 The initial calibration verification standard should read within the established control limits If it does not reinject it if it still does not work recalibrate Revision 7 0 119 Anions Page 12 of 15 11 2 3 1 Load calibration standards on the autosampler 11 2 3 2 Inject eight calibration standards 11 2 4 Check an initial calibration verification stan
66. and MSD attempted twice that fails recovery criteria both times but passes precision criteria See also section 3 4 4 4 0 Initial Calibration 41 4 2 4 3 Acceptance is based on the Correlation Coefficient for linear curves the Coefficient of Determination for nonlinear curves or the percent RSD when response factors or calibration factors are used See specific methods for requirements If the above criteria are not met analysis cannot begin until the problem has been isolated and a valid calibration has been performed In addition if Initial Calibration Verification ICV samples are not within specified laboratory acceptance criteria the ICV may be reanalyzed If the Revision 7 0 Page 6 of 11 006 ICV is still out a new calibration must be performed Sample analysis must not begin prior to resolving this problem In some cases an autosampler run may be initiated prior to the end of a shift and then reviewed the next day In this case all samples must be rerun with a valid calibration If this is not possible samples must either be canceled or reported with the proper qualifier NCALh or NCALI 4 4 Under the following circumstances results may be reported 4 4 1 4 4 2 If the failed initial calibration check has a high bias samples that are non detects may be reported without a qualifier If the failed initial calibration check has a low bias samples that have a result greater than the maximum regulator
67. and greater than 10 mg L for batch acceptance Reportable sample results must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 of the measured raw concentration of the sample However blank results below the reporting limit are considered to be ND and will not require a note 4 AnMDL study is completed whenever major equipment or procedural changes are made Standards are spiked at 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit 55 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL Ihe average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 6 Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 7
68. as described in section 10 5 The dissolved oxygen depletion of seven replicates is tabulated See QA Manual for calculation Results must be below the reporting limit 12 6 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration of 4 mg L for BOD and cBOD Plant 3 mL of Standard Glucose Glutamic Acid solution from section Revision 5 0 I05 BOD Page 6 of 8 10 5 into a BOD bottle This is calculated as a 100 solution Acceptance ranges are 80 120 with a maximum RSD of 10 12 7 Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive batches or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 13 Calculations 13 1 For seeded samples D O2 By f BOD mg L D O 1 D O 2 By B2 f BOD mg L X1 W Where D O D O of diluted sample immediately after preparation D O D O of diluted sample after a 5 day incubation
69. blank in first clean up batch following florisil activation to demonstrate that there is no contamination Revision 4 0 O54 8081 Page 16 of 16 8 9 2 With each use of activated florisil carry a laboratory fortified blank through the clean up process 9 0 SAFETY 9 1 The following compounds have been tentatively identified as known or suspected carcinogens 4 4 DDT 4 4 DDD the BHC s and the PCB s 9 2 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined however each chemical compound must be treated as a potential health hazard Accordingly exposure to these chemicals must be reduced to the lowest possible level A reference file of material safety data sheets is available to all personnel involved in the chemical analysis 9 3 See SOP 502 Compressed Gas Cylinder Handling SOP S03 Spill Control Policy 10 0 DEFINITIONS 10 1 See SOP Q15 SOP Definitions 11 0 CORRECTIVE ACTION FOR OUT OF CONTROL UNACCEPTABLE DATA 11 1 See SOP Q06 Corrective Action 12 0 POLLUTION PREVENTION AND WASTE MANAGEMENT 12 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP S07 Pollution Prevention 13 0 METHOD PERFORMANCE 13 1 See Method 8081B Tables 9 16 13 1 1 Our intralaboratory generated data is expected to achieve similar results Refer to MDL studies and laboratory control charts maintained in the QC Office 14
70. can occur with high dissolved solids is salt buildup at the tip of the nebulizer which affects aerosol flow rate and causes instrumental drift This problem is controlled by diluting the sample when necessary Also it has been reported that better control of the argon flow rates especially for the nebulizer improves instrument stability and precision this is accomplished with the use of mass flow controllers Chemical interferences include molecular compound formation ionization effects and solute vaporization effects Normally these effects are not significant with the ICP AES technique If observed they can be minimized by careful selection of operating conditions such as incident power and Revision 4 1 Page 5 of 21 M07 200 7 observation height by buffering of the sample by matrix matching and by standard addition procedures Chemical interferences are highly dependent on matrix type and the specific analyte element 4 4 Memory interferences are controlled by the use of a rinse blank between analyses The instrument automatically increases the rinse time following a high sample If a memory interference is still suspected the sample is re analyzed after the system is free of contamination 4 4 1 4 4 2 5 0 SAFETY Necessary rinse times for a particular element are estimated This is achieved by aspirating a standard containing elements at a concentration near the top of the linear dynamic range The aspiration
71. carefully to be certain that the procedure is followed correctly A new LCS may be considered as part of the original batch as long as 24 hours has not been exceeded from the start of processing of the first sample and the start of processing of the new LCS If a new LCS is processed conditions must be identical to those conditions under which the samples were prepared and analyzed 1 3 Ifthe problem is still not corrected check with the supervisor for advice before proceeding with the analysis 1 4 Ifthe noncompliant LCS is discovered after the analysis is completed an out of control qualifier must be placed on the LCS QLout Batch data may be accepted if 1 4 1 The problem does not appear to have affected the entire run AND one of the following is true 1 4 1 1 A MS or MSD from a noncalibration source fell within the LCS laboratory acceptance criteria QL MS Samples may be released without a qualifier 1 4 1 2 There is reasonable evidence documented with the raw data to suspect that the spiking solution was made incorrectly If possible evaluate recovery based on the new spiking level Samples may be released without a qualifier If this is not possible place QLout and QFspk on the LCS Revision 7 0 Page 2 of 11 1 4 2 006 1 4 1 3 Management deems the run reportable In this case each sample in the batch is reported with the proper qualifier attached NLOhi or NLOlo If it is uncertain whether the problem affecte
72. caused by equilibrium changes There must be correction for drift caused by temperature variations Revision 5 0 125 Page 2 of 8 5 2Coatings of oily material or particulate matter can impair electrode response These coatings can usually be removed by gentle wiping or detergent washing followed by D I water rinsing An additional treatment with hydrochloric acid 1 9 may be necessary to remove any remaining film 5 3Helpful Hints Allow sufficient time for temperature of sample to equilibrate in water bath 6 0 Safety Issues specific to the method General laboratory safety precautions are sufficient for this test 7 0 Instrumentation Equipment 7 lO0rion Model 720 pH ISE Meter 7 2Electrode An electrode with special low sodium error glass is recommended Orion Ross combination probe 8156 7 2 1VWR4 34107 377 7 3Water bath and tubes 7 3 1 Tubes are cleaned immediately after use by thorough rinsing with three portions of D I water and stored upside down to dry Note If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 7 4 Thermometer 8 0 Standards and Reagents 8 1 pH buffers 4 7 and 10 purchased premixed from a certified vendor Buffers are stored at room temperature Manufac
73. component of the Lake Elsinore and Canyon Lake Nutrient TMDL monitoring program are described in the 2006 Monitoring Plan The sampling process design schedules as laid out in the Monitoring Plan are summarized as follows San Jacinto Watershed Nutrient TMDL Monitoring Program Details of this program element can be found in the Appendix D Lake Elsinore Canyon Lake TMDL Compliance Program San Jacinto River Watershed Sampling Plan Lake Elsinore Nutrient TMDL Monitoring Program The sampling process design schedules required by the Lake Elsinore Nutrient TMDL Monitoring Plan are described in Section A6 of this QAPP Canyon Lake Nutrient TMDL Monitoring Program The sampling process design schedules required by the Canyon Lake Nutrient TMDL monitoring plan are described in Section A6 of this QAPP SJR Component The sampling process design schedule required by the SJR Component Program is the same as described above for the Canyon Lake Nutrient TMDL monitoring program described in Section A6 of this QAPP SJRIPP The sampling process design schedules required by the SJRIPP are described in Section A6 of this QAPP San Jacinto QAPP For all components of the San Jacinto QAPP should the sampling sites become inaccessible due to weather or other unforeseen factors alternative sites with similar characteristics will be selected If no alternative sites are available sampling will be conducted on another day to ensure the complet
74. fortified sample concentration C sample background concentration s concentration equivalent of analyte added to fortify the sample 9 4 4 If recovery of any analyte falls outside the designated range and laboratory performance for that analyte is shown to be in control Sect 9 3 the recovery problem encountered with the fortified sample is judged to be matrix related not system related The data user should be informed that the result for that analyte in the unfortified sample is suspect due to either the heterogeneous nature of the sample or an uncorrected matrix effect 9 4 5 Laboratory Fortified Matrix Duplicates LFMD or Matrix Spike Duplicates MSD are analyzed every 20 samples per matrix type per sample batch RPD must be 20 9 4 6 Internal standards responses The analyst is expected to monitor the responses from the internal standards throughout the sample set being Revision 3 0 M12 200 8 Page 16 of 26 analyzed Ratios of the internal standards responses against each other should also be monitored routinely This information may be used to detect potential problems caused by mass dependent drift errors incurred in adding the internal standards or increases in the concentrations of individual internal standards caused by background contributions from the sample The absolute response of any one internal standard must not deviate more than 60 125 of the original response in the calibration standard If deviati
75. held up to 6 months before analysis 8 2 For the determination of the dissolved elements the sample must be filtered through a 0 45 um pore diameter membrane filter at the time of collection or as soon thereafter as practically possible Glass or plastic filtering apparatus are recommended to avoid possible contamination If the filtered blank shows a problem with the glass apparatus only plastic apparatus should be used when the determinations of boron and silica are critical Use a portion of the filtered sample to rinse the filter flask discard this portion and collect the required volume of filtrate Acidify the filtrate with 1 1 nitric acid immediately following filtration to pH 2 8 3 For the determination of total recoverable elements in aqueous samples samples are not filtered but acidified with 1 1 nitric acid to pH lt 2 normally 3 mL of 1 1 acid per liter of sample is sufficient for most ambient and drinking water samples Preservation may be done at the time of collection however to avoid the hazards of strong acids in the field transport restrictions and possible contamination it is recommended that the samples be returned to the laboratory within two weeks of collection and acid preserved upon receipt in the laboratory The pH of all preserved samples is verified upon receipt by the laboratory and if necessary additional acid is Revision 4 1 7 200 7 Page 9 of 21 8 4 8 5 8 6 added to bring t
76. high sensitivity of ICP MS high purity reagents are used whenever possible All acids used for this method are of ultra high purity grade Nitric acid is preferred for ICP MS in order to minimize polyatomic ion interferences Several polyatomic ion interferences result when hydrochloric acid is used Table 2 however it should be noted that hydrochloric acid is recommended to maintain stability in solutions containing antimony and silver When hydrochloric acid is used corrections for the chloride polyatomic ion interferences must be applied to all data 7 1 Nitric acid concentrated sp gr 1 41 stored at room temperature for up to 10 years 7 2 Nitric acid 1 1 for rinsing Add for example 100 mL conc nitric acid to 100 mL of reagent grade water in a beaker Prepare fresh daily 7 1 3 Hydrochloric acid concentrated sp gr 1 19 stored at room temperature for up to 10 years Reagent Water All references to reagent grade water in this method refer to nanopure water Suitable water is prepared by passing distilled water through a mixed bed of anion and cation exchange resins and then through the Nanopure system to 18 mega ohm purity Standard Stock Solutions High purity stock solutions 10000 1000 100 20 or 10 ppm are purchased from reputable commercial sources Most metals are Revision 3 0 M12 200 8 Page 8 of 26 7 4 TO 7 6 7 7 purchased as a mixture however Hg and Sn are purchased separately
77. indicate a problem with a mixed standard each stock solution should be analyzed separately to determine the problem There can be slight high bias of Fe Al or other metals in mixed standards since stock sources of some metals contain trace amounts of other metals If this bias causes QC samples to be out of range each stock standard will be tested for the bias and this bias will be added to the true value of the metal in the standards 7 7 Blanks Four types of blanks are required for the analysis The calibration blank is used in establishing the analytical curve the laboratory reagent blank is used to assess possible contamination from the sample preparation procedure the laboratory fortified blank is used to assess routine laboratory performance and a rinse blank is used to flush the instrument uptake system and nebulizer between standards check solutions and samples to reduce memory interferences 7 1 1 The calibration blank for aqueous samples and extracts is prepared by acidifying reagent water to the same concentrations of the acids as used for the standards The calibration blank is stored in a contaminant free plastic bottle 7 1 2 The laboratory reagent blank LRB method blank MB must contain all the reagents in the same volumes as used in the processing of the samples The LRB is carried through the same entire preparation scheme as the samples including sample digestion when applicable 7 7 3 The laboratory fortified blank
78. is cleaned immediately prior to and after use by thorough rinsing with three portions of water If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 9 0 Standards 0 01M KCl Lab Control 0 7456 g KCl predried in 105 oven dissolved in 1 liter of Nanopure water This solution is stored at room temperature for up to 6 months 10 0 Procedure 10 1 Prepare dishes by heating at 180 C for a minimum of 1 hour 10 2 Take hot dishes out of 180 C oven Cool 15 20 minutes on a counter 10 3 Cool dishes to room temperature in a desiccator at least half an hour Weigh dishes on balance for tare weight and record Place dishes on water bath 10 4 Place a small amount of sample into a tube for electrical conductivity screening Samples that are high in salts TDS will have an elevated conductivity Filter the appropriate aliquot of sample to give a result of less than 2000 mg L prior to dilution factors Estimated Ec mLs of sample to analyze 001 200 200 200 2000 100 2001 4000 50 4001 8000 25 8001 20 000 10 220 000 See supervisor 10 5 Measure proper aliquot of well shook sample usually 100 ml into 100 ml graduated cylinder and filter Revision 5 0 I29 TDS Page 10 10 10
79. is lab packed for disposal by a professional waste hauler Revision 3 0 Page 8 of 8 A06 180 Table 1 Splitter Documentation Codes CODE Y UNP S N OH lt 2 gt 12 NS Pb X TS REC gt COD or C Approved by Susann K Thomas Date SPLITTER S KEY Special instructions have been followed Unpreserved Pres w sulfuric acid Pres w nitric acid Pres w sodium hydroxide pH could not be adjusted low enough matrix pH could not be adjusted high enough matrix Filtered Composited Pres w EDA Negative for sulfide Positive for sulfide lead carbonate added Negative for chlorine Positive for chlorine sodium thiosulfate added Received Split into another bottle or vial Extra added to already pres bottle or vial Bottle for Color Odor Turbiditiy only Cod vial Bottle for nitrate only Cyanide bottle Oil and grease bottle Total Petroleum Hyderocarbon bottle Phenol bottle 05 28 06 Revision 6 0 B02 MTF Page 1 of 9 COLIFORMS BY MULTIPLE TUBE FERMENTATION SM 9221 B C E E S BABCOCK STANDARD OPERATING PROCEDURE Effective Date 1 0 Scope and Application 1 1 1 2 1 3 14 1 5 The coliform group consists of several genera of bacteria belonging to the family Enterobacteriaceae This group is defined as all aerobic and facultative anaerobic gram negative nonspore forming rod shaped bacteria that fe
80. is less than 10ppm Place 40ml vials on the autosampler rack Use graduated cylinders if vials are not provided or if a dilution is needed to measure 20 mL of aqueous sample into 40mL vials If sample contains solid material that is larger than autopipet tip or autosampler needle then use the Tissue Tearer see section 6 2 Make sure to put the cover on the rack Press Start then Stand by verify vial numbers press ok Revision 5 0 26 Page 6 of 9 9 1 16 Uncheck acid addition box before starting 9 1 17 After the run is finished and the data has been reviewed select Print under the file menu 9 2 Solid sample preparation 9 2 1 Dry approximately 2g of solid or sludge sample in the 105 C oven overnight Note For solid samples note weight before and after oven as well as pan weight to determine total solid result 9 2 2 Crush and sieve dried sample using mortar pestle and 60 mesh sieve 9 2 3 Place 0 5g sample into a ceramic boat 9 2 4 Add 10 drops of HCl and 10 drops of Nanopure to sample to eliminate inorganic carbon 9 2 5 Dry on the hot plate 9 2 6 Dry in 180 C oven for about 2 hours to eliminate 9 2 7 Cool sample 9 2 8 Place boat directly into instrument for analysis 9 2 9 Reporting 9 2 9 1 Sludges are reported on a dry weight basis 9 2 9 2 Solid are reported on an as received basis Results must be calculated back to the original sample 96 TOC on dry sample x 46 solids 100 on AAR samp
81. is used all reportable results for target analytes must be qualified if that analyte was outside 15 criteria See Q06 for additional details 7 4 Gas chromatographic analysis of sample extracts 74 1 1 4 2 7 4 3 The breakdown of DDT and endrin should be measured before samples are analyzed and at the beginning of each 12 hour shift DDT and endrin are easily degraded in the injection port Breakdown occurs when the injection port liner is contaminated with high boiling residue from sample injection or when the injector contains metal fittings Check for degradation problems by injecting a standard containing only 4 4 DDT and endrin Presence of 4 4 DDE 4 4 DDD endrin ketone or endrin indicates breakdown If degradation of either DDT or endrin exceeds 15 take corrective action before proceeding with calibration Calculate percent breakdown as follows sum of degradation peak areas DDD DDE breakdown of DDT x 100 sum of all peak areas DDT DDE DDD sum of degradation peak areas aldehyde ketone breakdown of endrin __ x100 sum of all peak areas endrin aldehyde ketone 7 4 1 1 Injector maintenance and recalibration should be completed if the breakdown is greater than 15 for either compound The same GC operating conditions used for the initial calibration is employed for samples analyses The calibrat
82. noted on the schedule and entered into LIMS by editing the primary prep volume 12 5 Calculations associated with this method 12 5 1 Total Anions TA mequiv of OH HCO3 SO4 CI NO3 TA 12 5 2 Electrochemical Balance ECB Total Cations TC Total Anions TA 12 5 3 Total Dissolved Solids by Summation TDSSUM mg L of 0 6 Total Alkalinity Na Ca Mg SO4 Cl F 5103 TDSSUM 13 0 Transferring Data 13 1 Update the Schedule Run Log PeakNet Main Menu Schedule Schedule Analyst will usually make notes on the printed schedule the night before for Revision 7 0 119 Anions Page 14 of 15 such things as dilution changes sample bottle letters and referenced samples for spikes These things are not generally typed in initially because they are not always known for sure when they start loading the ICs 13 2 Reference Batch QC on Bench Sheet Element Laboratory Bench Sheet Batch Source sample s for MS MSD s are referenced Dilutions are entered by editing the Initial column with the appropriate amounts for a Final amount of 50mL for solids any dilution on top of the normal 1 10 extraction is entered in the Diln column of the Data Entry Review screen Spike Amounts and Spike IDs are entered 13 3 Create a Data Entry Table Element Laboratory Data Entry Review Batch Select the analytes associated with the batch click Create click Export and select an Elmnt User File to save th
83. of field staff data management and quality control and interactions with consultants associated with the SJRIPP trash monitoring program The organizational structure of the SJRIPP is diagramed in Figure 2 Water Quality monitoring associated with this program will focus on identifying and characterizing dumping locations within the project area Chemical monitoring will only be conducted if an opportunity presents itself that would justify the expense such as if a dump site is discovered within flowing receiving waters Chemical monitoring performed by the SJRIPP will follow this QAPP for laboratory analysis and quality assurance Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 8 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Figure 2 Organizational Chart amp Responsibilities San Jacinto River Improvement and Protection Program Santa Ana RWQCB Grant Manager David Woelfel Santa Ana RWQCB Quality Assurance Pavlova Vitale SJRIPP Program Administrator Monitoring Program Manager Alex Gann Clean Up Event Monitoring Aerial Photography Site Characterizations Program Manager Program Manager Program Manager County EH Jason Uhley Lou Pizatella Chemical Monitoring Program Manager Steve Clark San Jacinto River Watershed Component of the Santa Ana Integrated Watershed Plan The SJRWC was awarded a Proposition 50 Chapter 8 Planning Grant to develop the San Jacinto River Component of the Santa Ana Integrated Wa
84. performance cannot be verified the source of the problem is identified and corrected before either proceeding on with the initial determination of method detection limits or continuing with on going analyses 9 2 4 Method detection limit MDL MDL s are established whenever there is a change in instrumentation or a major modification to the analysis The MDLs must be sufficient to detect analytes at the required levels according to compliance monitoring regulation Sect 1 2 Method detection limits MDL are established for all analytes using reagent water blank fortified at various concentrations for example 0 1 ppb 0 5 ppb 0 625 ppb amp 2 5 ppb for drinking waters and 0 5 2 amp 10 ppb for wastewater The level that performs the best and most closely represents a concentration approaching 2 5 times the estimated detection limit EDL is chosen To determine MDL values take seven replicate aliquots of the fortified reagent water and process through the entire analytical method Perform all calculations defined in the method and report the concentration values in the appropriate units Calculate the MDL as follows MDL t x S where t Student s t value for a 99 confidence level and a standard deviation estimate with n 1 degrees of freedom t 3 14 for seven replicates S standard deviation of the replicate analyses NOTE Ifadditional confirmation is desired reanalyze the seven replicate aliquots on
85. prior to analysis may be stored in the extraction refrigerator R3 or the refrigerator in the main organics laboratory R4 or R5 After analysis extracts are either dumped out kept on lab bench or in one of the above refrigerators depending on the nature of the analytes 16 7 5 Digests 16 7 5 2 Metals stored on multilevel cart near metals samples 16 7 5 3 Kjeldahl prior to analysis may be stored under the Kjeldahl counter prior to bringing up to volume for a couple days Extracts are not stored after analysis 17 0 Sample Disposal 17 1 Inorganic Aqueous Samples 17 1 1 Unpreserved Stored for 5 6 weeks and then dumped into an empty barrel The pH is checked adjusted if necessary and then the contents are pumped down the sink 17 1 2 Preserved See ESB SOP S05 Neutralization Procedure for Acid and Alkaline Wastes 17 2 Soil Solid Sludge and Nonaqueous Liquid Samples 17 2 1 Nonhazardous Samples are kept for 3 months and then placed in the dumpster 17 3 Hazardous 17 3 1 Supervisors or chemists reviewing sample results will note when a sample exceeds hazardous limits by placing a red sticker on the sample with the hazardous constituent s name The sample is recorded in a notebook 17 3 2 The notebook includes the sample number date and initials of the person recording the sample the hazardous constituent name and concentration 17 3 3 After 3 months the sample is placed downstairs until it
86. recovery of various analytes Spikes will contain analytes at the level present in the sample or at the concentration of the mid range calibration standard whichever is higher Spike recovery will be calculated as follows Recovery A Ao S 100 Where A is the amount of analyte in the spiked sample Ao is the amount of analyte in a non spiked sample and S is the amount of spike added Control limits of 80 to 120 percent will be used for percent recovery Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 20 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Matrix spike replicates one duplicate per 20 samples or one per batch whichever is more frequent will be used to assess method precision A control limit of less than 25 percent will be used for relative difference Completeness Completeness is the measure of the amount of valid data obtained from a measurement system relative to the amount of data scheduled for collection under correct normal conditions Completeness measures the effectiveness of the overall investigation in collecting the required samples completed the required analyses and producing valid results Completeness will be calculated using the following equation Completeness number of valid data points total number of measurements 100 Field Data Completeness Field completeness is a quantitative measure of the actual number of samples collected compared to those samples scheduled for coll
87. response must be greater than method blank response to verify the Level of Detection or MDL 102 5 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Revision 5 0 I27 OP Page 7 of 9 Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL The average percent recovery of the samples must be 80 120 with a maximum RSD of 10 10 6 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 11 0 Calibration T9 gal A six point curve plus the zero point required by the method is analyzed on a yearly basis covering the referenced concentration range 2 An acceptable curve yields an r 0 99 or better 2 A regression equation is generated from the curve 4 Results are calculated from the regression equation 25 Immediately following calibration a 0 5mg L ICV is analyzed using the
88. run for the calibration Revision 7 0 Page 10 of 15 10 4 2 119 Anions blank One of these blanks is reported for every 20 samples to satisfy the method blank requirement Results must be below but not more negative than the reporting limit Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a note 10 5 Lab Control 10 5 1 10 5 2 10 5 3 In order to verify that standards have been prepared correctly a LCS is performed using a standard of known concentration from an independent source This laboratory control sample containing each analyte of concern is analyzed with each batch of samples processed If more than 20 samples are run in a batch analyze one LCS for every 20 samples and report per matrix type Evaluate the accuracy by comparing to laboratory acceptance criteria Results may be generated historically but must be as tight as 90 110 The acceptance criteria for PCBSA is 80 120 If acceptable data cannot be obtained locate the problem and correct it If during the course of a run a LCS is out of range it is rerun on the spot if possible If this is not possible the analyst may reevaluate the data based on peak height rather than peak area If this does not solve the problem a fresh calibration
89. same type does not require new study Revision 7 0 Page 13 of 14 6 1 2 001 The study is completed by the analysis of four replicates of a QC sample diluted in a clean quality system matrix at a concentration specified in the analytical SOP This level is taken from individual method requirements or in the absence of such requirements set at 1 4 times the LOQ or RL If analytes do not lend themselves to spiking QC or PT samples are used An analyst may exclude a data point from the study as long as it is proven to be a statistical outlyer This is determined using the Grubbs Test A 9596 confidence level is used to determine if a data point may be rejected The analyst must document this proof with the raw data All data is reported from the primary column or detector Results are compared to acceptance ranges specified in the SOP If limits for specific analytes are not found in the determinative method acceptance criteria may be taken from limits provided by Performance Testing Studies The analyst must successfully complete the study prior to analysis of client samples All work performed during the training period prior to a successful DoC must be co initialed by the trainer If the analyst is joining a cell the DoC consists of a cell change form The analyst must turn in valid LCS and method blank data from four consecutive batches of the training period LCS and MB results must meet laboratory prescribed acceptance c
90. sample is spiked at a level of not more than 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QCS sample made at a concentration 5 50 times the MDL or as of August 2006 1 4 times the Level of Quantitation RL per 2003 NELAP Standards The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 20 Revision 5 0 145 Page 9 of 10 10 6 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 10 7 Performance Evaluation Studies are performed twice a year A QCS sample acquired from an independent source such as ERA is analyzed Acceptance criteria supplied by the manufacturer is used to access performance 11 0 Calculations 11 1 The instrument compares peak areas of samples rather than peak height against the calibration curve Raw results are transferred into LIMS 11 1 1 Di
91. solution containing 5 2596 NaOCI such as Clorox Buffer Disodium ethylenediamine tetraacetate EDTA 7 5 Dissolve 18 75g of EDTA disodium salt and 0 5g of NaOH in 250ml of D I water This solution is stored for up to 6 months at room temperature Sodium nitroferricyanide 0 2 Dissolve 0 5g of sodium nitroferriocyanide in 250ml of D I water This solution is stored for up to 6 months at room temperature 1 N NaOH Dissolve 40g of NaOH into 1L of D I water This solution is stored for up to 6 months at room temperature 0 04N Sulfuric Acid Add 1 12mL of concentrated sulfuric acid into 1L of D I water This solution is stored for up to 6 months at room temperature Borate Buffer 6 9 1 0 1 N NaOH Dissolve 4g of NaOH into 1L of D I water 6 9 2 Mix 0 95g Na2B407 10H50 into 100mL of Nnaopure water 6 9 3 Add 8 8 mL of 0 1N NaOH and 50 mL of borate solution into a 100 mL flask and bring up to volume with D I water 6 9 4 This solution is stored for up to 6 months at room temperature Revision 5 0 153 NH3 Page 4 of 10 Note The above reagent recipes are specified by the instrument manufacturer SEAL Analytical AQ2 Method No EPA 103 A Rev 4 O 6 01 05 and by Standard Methods 20 Edition 4500 NH 7 0 Standards and Quality Control Requirements Note See also ESB SOP 01 for general QC requirements 7 1 Lab Control Sample LCS 7 1 1 Stock Solution EM 1000 mg L NH3 Standard stored at room temperature
92. the run Target analytes in the SIC solution must be within 2096 of expected value and less than the RL in the SIC blank to verify the correction routine If SIC blank is high see section 9 5 1 for qualifying criteria interelement spectral correction factors are updated if the SIC solution and SIC blank do not consistently meet acceptance criteria To update correction factors separate standards of each metal are analyzed at a level of 100ppm except Fe 300ppm and AI 200ppm Target metals are examined for any false response caused by the elevated metal 9 6 Assessing Analyte Recovery and Data Quality 9 6 1 9 6 2 9 6 3 Laboratory Fortified Matrix LFM or Matrix Spike MS Sample homogeneity and the chemical nature of the sample matrix can affect analyte recovery and the quality of the data Taking separate aliquots from the sample for replicate and fortified analyses can in some cases assess the effect The laboratory adds a known amount of each analyte for every 20 routine samples per matrix type per batch When combined with the MSD see section 9 6 5 this constitutes a frequency of 10 In each case the LFM aliquot is a duplicate of the aliquot used for sample analysis and for total recoverable determinations added prior to sample preparation The added analyte concentration is the same as that used in the laboratory fortified blank See section 7 7 3 for recipe Samples are chosen at random Calculate the percen
93. the sample batch contains only undistilled samples 7 3 3 Acceptability MB must read below but not more negative than the RL of 0 1 mg L for batch acceptance Samples results reported must be accompanied with a note if the method blank exceeds a concentration greater than 1 10 of the measured raw concentration Revision 5 0 153 NH3 Page 5 of 10 of the sample however blank results below the RL are considered to be ND and will not require a note Note The blank value noted in the NBLK qualifier is the raw blank result If the sample being qualified was diluted in addition to NBLK the analyst must also attach the qualifier NBLKd which includes the sample raw result Note Since the intensity of the color used to quantify the concentration is pH dependent the acid concentration of the diluant and the standard ammonia solutions should approximate that of the samples 7 4 Calibration Standard 7 4 Stock Ammonium chloride NH4CI 7 4 2 Intermediate Standard 1000ppm 7 4 2 1 Dehydrate Ammonium Chloride NH4CI in a 105 C oven 7 4 2 2 Allow salt to cool in a dessicator Weigh out 3 819 g NHACI 7 4 2 3 Dilute to 1 liter with D I water in a volumetric flask containing 1 mL sulfuric acid 7 4 2 4 Pour the solution into a 1 liter amber bottle Keep at room temperature out of sunlight This standard may be kept for up to 1 year or replaced sooner if comparison with QC samples indicate a problem 7 4 3 Intermediate standard SOppm D
94. the sample may contribute deposits of material on the extraction and or skimmer cones reducing the effective diameter of the orifices and therefore ion transmission Dissolved solids levels not exceeding 0 2 w v have been recommended to reduce such effects Brine samples are routinely diluted Internal standardization may be effectively used to compensate for many physical interference effects Internal standards ideally should have similar analytical behavior to the elements being determined 4 1 5 Memory interferences Result when isotopes of elements in a previous sample contribute to the signals measured in a new sample Memory effects can result from sample deposition on the sampler and skimmer cones and from the buildup of sample material in the plasma torch and spray chamber The site where these effects occur is dependent on the element and can be minimized by flushing the system with a rinse blank between samples Sect 7 6 3 The possibility of memory interferences is recognized within an analytical run and suitable rinse times are used to reduce them The rinse times necessary for a particular element are estimated and monitored by the analysis of a blank following the 500ppb linearity check at the end of every run Memory interferences may also be assessed within an analytical run by using a minimum of three replicate integrations for data acquisition If the integrated signal values drop consecutively the analyst is alerted to the
95. the vial less sample must be used If sample turns turbid or precipitates see section 4 1 Choose dilutions according to sample color clearness and odor Mark the amount of sample used on the COD prep sheet Add Nanopure water to bring up QC samples and any diluted samples up to 2mls Verify that the liquid level is the same throughout the batch 8 6 Cap tightly and shake to mix layers A thorough mixing is necessary before heating to prevent local heating of sulfuric acid layer on bottom of tube that may cause an explosive reaction 8 7 Process standards and blanks exactly as the samples 8 8 Place in oven or block digester at 150 C for two hours Set timer for 120 minutes Leave tubes in reactor for approximately 20 minutes after timer goes off 8 9 Invert cooled samples several times Return vials to rack until cool to the touch approximately 30 minutes before measuring absorbance Dislodge solids that adhere to container by gently tapping If sample is turbid let it settle longer use a centrifuge or reanalyze with less sample volume 8 10 Measure color intensity on Genesys 10uv by setting the spec to read at 620 nm On the spec select Set nm and enter 620 This wavelength was determined to be optimal for our laboratory conditions 8 11 Check the digested reagent blank by placing a vial containing 5mls of Nanopure into the spec Set transmittance to 100 by selecting Change Mode until T appears and then select Measure Blank
96. transducer thermister DO probe turbidity sensor and pH electrical conductance EC and oxidation reduction ORP electrodes connected to a Surveyor 4 data display controller or equivalent via a 15 m waterproof cable The DataSonde4a will be calibrated each morning before leaving for the lake results will be recorded in a calibration log The DO probe will be calibrated against an 02 saturated water sample prepared by sparging with lab air the pH electrode will be calibrated against pH 7 and 10 buffers EC will be calibrated against a standard KCI solution ORP will be calibrated against quinhydrone and turbidity will be calibrated against a turbidimetric standard following Standard Methods APHA 1998 Table 8 The temperature sensor and pressure transducer will not be calibrated although they will be confirmed as working properly and within specification by the factory The transparency of the lake at the sampling sites will be measured using a Secchi disk Field data will be recorded at the time of sampling in field logs that will be transferred to an Excel spreadsheet in the lab B8 INSPECTION ACCEPTANCE REQUIREMENTS FOR SUPPLIES AND CONSUMABLES Contract Laboratories will supply all the sample containers and other consumable supplies necessary for the Lake Elsinore and Canyon Lake Nutrient TMDL or SJRIPP Monitoring Program All laboratories contracted by the TASK FORCE and or SJRIPP will operate using quality assurance and quality con
97. two more nonconsecutive days and again calculate the MDL values for each day An average of the three MDL values for each analyte may provide for a more appropriate MDL estimate If the relative standard deviation RSD from the analyses of the seven aliquots is 10 the concentration used to determine the analyte MDL may have been inappropriately high for the determination If so this could result in the calculation of an unrealistically low MDL Concurrently determination of MDL in reagent water represents a best case situation and does not reflect possible matrix effects of real world samples However successful analyses Revision 3 0 M12 200 8 Page 12 of 26 of LFMs Sect 9 4 can give confidence to the MDL value determined in reagent water 9 2 4 1 LOD Verification On a yearly basis a QC sample is spiked at a level of not more than 1 4 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL for each instrument 9 2 5 Analyst Demonstration of Capability Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 1 4 times the RL The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 9 2 5 1 Studies in the past have been performed at
98. used for data acquisition The average of the integrations is used for instrument calibration and data reporting Analyze a 1 ppb 0 25ppb Hg standard at the reporting limit Results should be 50 150 Analyze a 100ppb and if needed a 250ppb or 500ppb standard to verify linearity Results should be 10 of the expected value 10 5 The rinse blank is used to flush the system between solution changes for blanks standards and samples Allow sufficient rinse time to remove traces of the previous sample Sect 4 1 5 Solutions should be aspirated for 30 sec prior to the acquisition of data to allow equilibrium to be established Revision 3 0 M12 200 8 Page 18 of 26 11 PROCEDURE Note Due to occasional client requests for lower RL s the analyst may vary prep amounts 11 1 Aqueous Sample Preparation Dissolved Analytes Refer to Sample Prep SOP M02A 11 2 Aqueous Sample Preparation Total Recoverable Analytes Refer to Sample Prep SOP M02A 11 5 Samples with turbidity 1 NTU are prepared as follows Add the following to a sample tube water liquid internal standard 50 uL 50 uL sample 5mL 2 mL 4 HNO 2 acid water 5mL 5mL Nanopure 0 mL 3mL 11 4 Sample Analysis 11 4 1 For new or unusual matrices samples are often prediluted 11 4 2 Initiate instrument operating configuration Tune and optimize the instrument for the analytes of interest Follow ELAN 6000 or 9000 software instructions 11 4 3 Establ
99. valuable tool for demonstrating the ability to perform the method acceptably Reference materials containing high concentrations of analytes can provide additional information on the performance of the spectral interference correction routine 9 7 Internal standards are used with all analyses Directions for using internal standard s are given in Section 11 2 4 9 8 A Detection Limit Check is analyzed with every calibration at the detection limit concentration 50 150 of the expected value is considered acceptable 10 0 CALIBRATION AND STANDARDIZATION 10 1 Specific wavelengths are listed in Table 2 Other wavelengths may be substituted if they can provide the needed sensitivity and are corrected for spectral interference Instrument Operating Conditions The analyst follows the instructions provided by the instrument manufacturer unless other conditions provide similar or better performance for a task 10 1 1 Prior to using this method optimize the plasma operating conditions using the 10 mg L manganese solution and the autotune program provided with the software 10 1 2 Calibrate the instrument per manufacturers instructions using a single point calibration 10 2 Before using the procedure Section 11 0 to analyze samples there must be data available documenting initial demonstration of performance The required data and procedure is described in Section 9 2 This data must be generated using the same instrument operating conditions an
100. work pricing in Element and for each invalid result find the login number and change the BOD price to 0 14 3 3 2 Print a copy of the bench sheet 14 3 3 3 Make two copies of every cancellation form one for Gail and the other for peer review Give the original to the project manager associated with that client 14 4 Turn in for peer review Original completed data page Copy of bench sheet Copies of BOD cancellation forms if applicable Completed BOD peer review sheet 14 5 The reporting units for this analysis are mg L 14 6 The raw result entered into LIMS is the sample depletion minus the method blank depletion see Note sec 13 14 7 The number entered in the DIL column in LIMS is the value 100 Revision 5 0 LOD BOD Page 8 of 8 percentage planted 14 6 Customers can refer to this SOP section 6 for temperature and duration of storage 15 Definitions See SOP Q15 SOP Definitions Seed Control Method Blank 16 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 17 Pollution Prevention and Waste Management 17 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes 17 2 SOP S07 Pollution Prevention 18 References Standard Methods for the Examination of Water and Wastewater APHA AWWA WPCF 18th edition 5210B EPA 405 1 EPA Methods for the Chemical Analysis of Water and Wastes Note All italicized items a
101. 0 01 5 ppb 6 7 pt Curve Methoxychlor OC EPA 8081 0 23 ug L 0 01 5 ppb 6 7 pt Curve Toxaphene OC EPA 8081 0 83 ug L 1 40 ppb 6 7 pt Curve Varies See organophosphate OP pesticides EPA 8141 Separate entries 4 50 ug L 5 7 point curve below Aspon OP EPA 8141 0 7 ug L 4 50 ug L 5 7 point curve Azinphos methyl OP EPA 8141 0 65 ug L 4 50 ug L 5 7 point curve Azinphos ethyl OP EPA 8141 0 66 ug L 4 50 ug L 5 7 point curve Bolstar Sulprofos OP EPA 8141 0 44 ug L 4 50 ug L 5 7 point curve Carbophenothion OP EPA 8141 0 4 ug L 4 50 ug L 5 7 point curve Chlorfenvinphos OP EPA 8141 1 4 ug L 4 50 ug L 5 7 point curve Chlorpyrifos OP EPA 8141 0 63 ug L 4 50 ug L 5 7 point curve Chlorpyrifos methyl OP EPA 8141 0 62 ug L 4 50 ug L 5 7 point curve Coumaphos OP EPA 8141 0 68 ug L 4 50 ug L 5 7 point curve Crotoxyphos OP EPA 8141 0 9 ug L 4 50 ug L 5 7 point curve Demeton O OP EPA 8141 1 2 ug L 4 50 ug L 5 7 point curve Demeton S OP EPA 8141 1 2 ug L 4 50 ug L 5 7 point curve Diazinon OP EPA 8141 0 73 ug L 4 50 ug L 5 7 point curve Dichlorofenthion OP EPA 8141 0 51 ug L 4 50 ug L 5 7 point curve Dichlorvos DDVP OP EPA 8141 0 82 ug L 4 50 ug L 5 7 point curve Dicrotophos OP EPA 8141 0 84 ug L 4 50 ug L 5 7 point curve Dimethoate OP EPA 8141 1 2 ug L 4 50 ug L 5 7 point curve Dioxathion OP EPA 8141 0 32 ug L 4 50 ug L 5 7 point curve Disulfoton OP EPA 8141 0 71 ug L 4 50 ug L 5 7 point curve EPN OP EPA 8141 0 67 ug L 4 50 ug
102. 0 ug L 5 7 point curve TEPP OP EPA 8141 0 49 ug L 4 50 ug L 5 7 point curve Terbufos OP EPA 8141 0 61 ug L 4 50 ug L 5 7 point curve Thionazin Zinophos OP EPA 8141 0 96 ug L 4 50 ug L 5 7 point curve Tokuthion Protothiofos OP EPA 8141 0 5 ug L 4 50 ug L 5 7 point curve Trichlorfon OP EPA 8141 0 39 ug L 4 50 ug L 5 7 point curve Trichloronate OP EPA 8141 0 61 ug L 4 50 ug L 5 7 point curve Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Page 35 Table 11 Analytical Methods Lake Elsinore and Canyon Lake Nutrient TMDL Monitoring Parameter Analytical Operating Range Calibration Method Limit Method Field Analyses dissolved oxygen DO 4500 O 0 1 mg L 0 1 20 mg L Air Sat d Water water temperature 2550 B 0 1 C 4 35 N A specific conductance 2510 B 0 01 mS cm 0 01 50 mS cm Standards pH 4500 H 0 01 2 12 Buffers turbidity 2130 B 0 1 NTU 0 1 100 NTU Standards water clarity secchi depth N A 0 1 m 0 1 30m N A oxidation reduction potential 2580 B 1 300 800 mV Standards Laboratory Analyses ammonia nitrogen NH4 N 4500 NH3 0 04 mg L 0 04 4 mg L Standards nitrate nitrite nitrogen NOs NO N 4500 NO3 F 0 04 mg L 0 04 4 mg L Standards total nitrogen TN 4500 N 0 04 mg L 0 04 4 mg L Standards soluble reactive phosphorus SRP 45
103. 00 P G 0 01 mg L 0 01 1 mg L Standards total suspended solids TSS 2540 D 5 mg L 5 100 mg L N A biochemical oxygen demand BOD 5210 B 3 mg L 3 100 mg L N A chemical oxygen demand COD 5220 D 10 mg L 10 1000 mg L Standards chlorophyll a 10200 H 3 0 1 ug L 0 1 1000 pg L Standards total phosphorus TP 4500 P 0 02 mg L 0 2 2 mg L Standards total dissolved solids TDS 2540 50 mg L 50 10 000 mg L N A total hardness 2340 B 0 1 mg L 0 1 300 mg L Standards dissolved organic carbon DOC 5310 C 5 mg L 5 100 mg L Standards total organic carbon TOC 5310 C 5 mg L 5 100 mg L Standards dissolved manganese Mna 0 007 mg L 0 007 50 mg L Standards dissolved iron Feziss N A 0 004 mg L 0 004 100 mg L Standards 3120 B 0 004 mg L 0 004 100 mg L Standards total iron Feria Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 36 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE B5 QUALITY CONTROL REQUIREMENTS Water quality samples collected under programs described within this QAPP will take care to ensure the collection of representative water samples laboratories contracted by the TASK FORCE will follow quality assurance and quality control programs in accordance with guidelines established by the State of California and the U S EPA Laboratories are required to submit a copy of their SOPs for laboratory quality control to the TASK FORCE Quality Assurance Manager for review and approval
104. 06 1 0 Scope and Application 1 1 1 2 This method covers the determination of ammonia in drinking surface and saline waters domestic and industrial wastes in the range of 0 1 to 2 0 mg L NH3 as N This range is for photometric measurements made at 660nm in a 10 mm tubular cell Higher concentrations can be determined by sample dilution This method may also be used for solid samples if both client and regulator agree to this variation Environmental Relevance Ammonia is present naturally in surface and wastewaters Its concentration is generally low in groundwaters because it adsorbs to soil particles and clays and is not leached readily from soils It is produced largely by deamination of organic nitrogen containing compounds and by hydrolysis of urea At some treatment plants ammonia is added to react with chlorine to form combined chlorine residual In the chlorination of wastewater effluents containing ammonia virtually no free residual chlorine is obtained until ammonia has been oxidized The chlorine reacts with ammonia to form mono and dichloramines 2 0 Summary of Method 2 1 Samples are distilled if under NPDES program or filtered and analyzed on an automated colorimetric system Alkaline phenol and hypochlorite react with ammonia to form indophenol blue that is proportional to the ammonia concentration The blue color formed is intensified with sodium nitroprusside 3 0 Sample Handling and Preservation 3 1 3 2
105. 0mg and 40mg quantities for calibration points of 0 296 0 896 1 696 2 496 and 3 296 carbon 8 5 1 2 Calibration checks Checks are performed every twenty samples and at the end of the run alternating between a level of 0 8 10 mg and 2 4 30mg Results must be within 80 120 of the expected value Second source Glucose 40 carbon at 99 5 purity 39 79 carbon purchased from a certified vendor This salt is stored at room temperature for up to 10 years 8 5 2 1 A LCS ICV is made by analyzing 20mg of glucose for a true value of 1 6 carbon based on a sample aliquot of 0 5g Results must be within 70 130 of the expected value 8 5 2 0 MS MSD is made by adding 20mg of glucose to 0 5g of sample for a spike concentration of 1 696 carbon Results must be within 27 119 based on historical data of the expected value with a maximum RPD of 25 Revision 5 0 Page 5 of 9 8 5 3 9 0 Procedure O26 TOC Method Blank A method blank is analyzed with each batch by weighing 0 5g of baked sand Results must be less than the reporting limit 9 Instrument set up 9 1 1 921 2 9 1 10 9 1 11 9 1 12 9 1 13 9 1 14 9 1 15 Make sure the instrument is set to PC Control switch found inside in the upper right of the instrument Turn on the instrument while holding the enter key on the front of the instrument This is a reset on stand alone mode usually the instrument stays on If you have just turned on
106. 1 2 Add 40 ml of D I water and 10 ml of lab control working standard to the second beaker 7 1 2 Use 3 beakers for the spiked sample Tad 22 In one beaker add 5 ml of sample filter all samples if not clear and 45 ml of D water Tella In the other two beakers Spike and Duplicate Spike add 5 ml of sample 10 ml of lab control working standard solution and 35 ml of D I water Revision 5 0 NO2 Page 4 of 6 122 7 1 3Set up the rest of the samples in beakers by adding 5 ml of sample and 45 ml of D water 7 1 3 1 If the sample is not clear filter it filtrate is discolored or turbid take a background reading Zero the spec to a blank prior to addition of color reagent Read the sample prior to addition of color reagent This absorbance is subtracted from the reading acquired in section 7 5 results are still out of range a serial dilution may be necessary 7 1 4 For solid samples Add an amount of water equal to ten times the weight material taken as a sample agitated for sixty minutes by shaking reagent of solid This mixture is intermittently Filter the resulting slurry through a 0 45 micron membrane type fil 1 5 ml of extract and 45 ml of D I water sample beaker Document the ratio used on page 7 2 Add 2 ml of the color reagent to each sampl Swirl Let sit for at least
107. 1 4 6 1 4 7 1 4 8 1 4 9 1 4 10 1 4 11 001 when analyte is normally present at high enough concentrations for precision analysis Check the SOP for the analysis in question to determine if a matrix spike is to be performed If for some reason the required sample volume is unavailable precision data may be taken from a LCSD Precision data is performed at a frequency that meets data quality Objectives or specified test method requirements Relative percent difference RPD and UCL are calculated by computer as indicated in the Quality Assurance Manual Quality control charts are available in LIMS for precision data indicating the RPD mean and UCL If recoveries do not fall below the UCL laboratory personnel should review laboratory techniques used in the procedure check for oddities in the matrix and ensure that the precision results were the best possible using the prescribed method See SOP Q06 for further corrective action requirements If it 1s still unclear how to proceed discuss the problem with the supervisor or QA Manager Duplicate samples may be analyzed for confirmation purposes as is the case for organic analyses of drinking water samples having a result at or above the reporting limit or liquid samples having a reportable result less than ten times the reporting limit If the result is confirmed by duplicate analyses attach N DUP or Nconf to the sample analyte Certain commonly occurring analytes like P
108. 10 8 3 8 4 8 5 8 6 8 7 8 8 8 9 8 10 8 11 8 12 0 I53 NH3 and at the end of the run to prove that the existing calibration is still valid Recovery must be 85 115 8 2 5 Calibration Check Blank Analyze a calibration blank prior to sample analysis every 10 sample and at the end of the run to prove that the existing calibration is still valid Results must be less but not more negative than the reporting limit 8 2 6 A standard at the reporting limit is analyzed at the end of the run This is used to evaluate instrument sensitivity should calibration checks show a low bias This standard should have a signal greater than the method blank Analyze samples on the SEAL Allow instrument to warm up Load standard reagents and samples See SEAL SOP 141 for general operating instructions Choose method and begin analysis When an acceptable calibration has been performed submit the tray of samples If diluted samples read below 0 1 mg L re analyze using more sample and diluting to a final volume of 50 ml Ideally diluted samples should not fall in the lower quarter of the calibration curve If any sample reads above 2 0 mg L re analyze using less sample Watch for possible carry over Studies have shown that carry over may occur over a concentration of 50mg L Rerun samples at or above the reporting limit following a sample at this concentration Be mindful of carry over that may happen in the distillatio
109. 10 5 2 If 25096 deviation occurs with an individual extract optimize instrument performance and inject a second aliquot of that extract 10 5 2 1 If the reinjected aliquot produces an acceptable internal standard response report results for that aliquot 10 5 2 2 If a deviation of greater than 50 is obtained for the reinjected extract extraction of the sample is repeated provided the sample is still available Otherwise report results obtained from the re injected extract with the proper qualifier Assessing Laboratory Performance Laboratory Fortified Blank 10 6 1 The laboratory analyzes one laboratory fortified blank LFB sample with every twenty samples per matrix type or one per sample set all samples extracted within a 24 h period whichever is greater A laboratory fortified blank duplicate may also be analyzed Acceptance ranges are generated from historical data and updated periodically in Element If recovery of gt 20 of the analytes falls outside the control limits that LFB is judged out of control and the source of the problem must be identified and resolved before continuing analyses Assessing Analyte Recovery Laboratory Fortified Sample Matrix Revision 4 1 Page 12 of 16 10 8 10 9 10 7 1 10 7 2 O53 8141 The laboratory adds a known concentration of analytes to a minimum of 596 of the routine samples per matrix type or one sample concentration per set whichever is greater A laboratory fortified sa
110. 100 100 Ti 334 94 3 8 3 8 5 10 1 2 TI 190 8 40 40 27 100 48 V 310 23 64 10 2 5 Zn 206 2 5 9 10 1 2 Run MDL at 2 5 times estimated MDL Revision 4 1 M07 200 7 Page 21 of 21 Table 3 Interfering Metals Analyte Wave length Ja Be Ca Mg Mn Mo Ni mi TI iV Ag 328 07 X X Al 396 15 x x x x x x x As 188 98 X X x x X x x x X X x x x B 249 72 X X Ba 233 53 x Be 313 11 x Cd 228 8 x Ca 317 93 Cd 228 80 Co 228 62 x x x x xX Cr 267 72 x x X Cu 327 39 x x X Fe 238 2 X x X K 766 49 Mg 285 21 Mn 257 61 x Mo 202 03 x Na 589 59 Ni 231 6 x x x Pb 220 35 x x x x X X x X X Sb 206 84 x x X X Se 196 03 x X x x X X X Tot Si 251 61 x x x Sn 189 93 x X Sr 407 77 x Ti 334 94 x TI 190 8 x X V 310 28 x x x x x x x X x x X X X x x Zn 206 2 x x x x X x This metal interferes with this analyte Spectral correction must be applied Revision 4 0 M12 200 8 Page 1 of 26 E S BABCOCK STANDARD OPERATING PROCEDURE FOR METHOD EPA 200 8 Effective Date 09 26 06 TITLE Determination Of Trace Elements In Waters And Wastes By Inductively Coupled Plasma Mass Spectrometry 1 SCOPE AND APPLICATION 1 1 This method provides procedures for determination of dissolved elements in ground waters surface waters an
111. 100 2 Amount of Sodium sulfite needed to destroy the residual Chlorine in the BOD sample Add this amount to fresh sample 11 1 2 Adjust pH to between 6 5 and 7 5 Check the pH with pH paper or meter Adjust acidic samples with 0 25 N NaOH 1g 100ml DI and basic samples with Sulfuric Acid 5 drops to 100ml DI Do not dilute by more than 0 5 about 10 drops 100 ml Use a higher concentration acid or base if more than 0 5 is needed to neutralize the sample or adjust the pH of the diluted sample 11 2 Sample Incubation and Analysis 11 2 1 Place 19 liters of Nanopure water into blue jug Add 1 ml each of Phosphate buffer Magnesium Sulfate Calcium Chloride and Ferric Revision 5 0 105 BOD Page 4 of 8 Chloride solutions per liter of water Aerate water in refrigerator until temperature reads 19 21 C Temperature of water will affect D O Regulate the temperature with a thermometer Fill up a bottle for unseeded blank then seed Nanopure water in the blue jug with 0 mL plant influent received in lab no longer than 24 to 48 hours preferably one to be run the same day if possible use as a duplicate Check with lab director When planting seed pipet sample out of unshaken bottle 11 2 2 Arrange bottles so two three dilutions of each sample can be made If the determination of D O is by probe then D O and D O are made from the same bottle so only one bottle is needed for each dilution Set up labeled bottles for blan
112. 100 ppb per the QCS level mentioned in 200 8 or at 20 ppb 9 2 6 Analyst Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive LCS s or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative Standard deviation between the four replicates must be less that or equal to 20 Performance Evaluation Studies are performed twice a year 9 3 Assessing Laboratory Performance mandatory 9 3 1 Laboratory reagent blank LRB The laboratory analyzes at least one LRB Sect 7 6 2 with each batch of 20 or fewer of samples of the same matrix LRB data are used to assess contamination from the laboratory environment and to characterize spectral background from the reagents used in sample processing For batch acceptance LRB values must be less but not more negative than 12 the reporting limit for all metals If the LRB is not acceptable fresh aliquots of the samples must be prepared and analyzed again for the affected analytes after the source of contamination has been corrected and acceptable LRB values have been obtained Samples results reported must be accompanied with a note if the method blank exceeds a concentration greater than 1 10 of the measured concentration of the sample or is greater than 1 10 of the specified regulatory limit if known However blank results below 1 2 the RL are cons
113. 108C 0 712 106C 2 Cr 1 000 52C 3 Co 1 000 59C Cu 1 000 63C Pb 1 000 206C 1 000 207C 1 000 208C 4 Mn 1 000 55C Mo 1 000 98C 0 146 99C 5 Ni 1 000 60C Se 1 000 82C 6 Ag 1 000 107C 1 000 205C Th 1 000 232C U 1 000 238C V 1 000 51C 3 127 53C 0 113 52C 7 Zn 1 000 66C Bi 1 000 209C In 1 000 115C 0 016 118C 8 Sc 1 000 45C Tb 1 000 159C Y 1 000 89C C calibration blank subtracted counts at specified mass 1 correction for chloride interference with adjustment for 77Se ArCl 75 77 ratio may be determined from the reagent blank Isobaric mass 82 must be from Se only and not BrH 2 correction for MoO interference Isobaric mass 106 must be from Cd only not Zro An additional isobaric elemental correction should be made if palladium is present 3 00 4 v v the background from CIOH will normally be small However the contribution may be estimated from the reagent blank Isobaric mass must be from Cr only not ArC 4 allowance for isotopic variability of lead isotopes 5 isobaric elemental correction for ruthenium 6 some argon supplies contain krypton as an impurity Selenium is corrected for 82Kr by background subtraction 7 correction for chloride interference with adjustment for 53Cr CIO 51 53 ratio may be determined from the reagent blank Isobaric mass 52 must be from Cr only no Ar
114. 12 0 Quality Control Note See also ESB SOP 001 for general QC requirements Laal Duplicates are analyzed daily or every ten samples per matrix type whichever is more The Relative Percent Difference is calculated and compared to the acceptance range Sample acceptability however is based on a maximum RPD of 20 If the RPD does not fall within this acceptance range the sample is re analyzed If the RPD still does not fall within the acceptance range a note is placed on the client s results L282 Laboratory Control An aliquot of the KCL standard is analyzed daily or one every twenty samples whichever is more and reported per matrix type The result from this analysis is compared to the control limit 90 110 recovery the result fall outside the control limit the analysis is considered to be out of control and all the other results in the analytical run are questionable Troubleshooting is performed to Revision 5 0 I29 TDS Page 7 12 12 12 12 1 2 12 of 8 attempt to determine the cause If the cause is not determined or the cause is something that could effect the other samples in the batch the analyses will be re run 3 A method blank is analyzed daily or one every twenty samples whichever is more and reported per matrix type 200 mL of water is filtered exactly like a sample It must read less than 10 mg L
115. 16 2 Methods of Chemical Analysis of Water and Wastes EPA 600 4 79 020 Method 360 1 and 360 2 Approved by Susann K Thomas Date 01 06 06 Revision 5 0 125 Page 1 of 8 pH Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE EPA 9040B 9045C SM 4500 H B Date Effective 10 30 06 1 0 Scope and Applications 1 1 This method is applicable for all aqueous solutions as a measure of the hydrogen ion activity of the sample This is important for all phases of water supply and wastewater treatment since almost all treatment processes are pH controlled 1 2 Natural waters usually have pH values in the range of 4 9 units and most are slightly basic due to the interaction with alkali and alkaline earth metals 1 3 Solid samples may be analyzed as described later in section 9 13 2 0 Working Range 1 to 14 units 3 0 Summary of Method This method determines the hydrogen ion activity by potentiometric measurement using a glass electrode The system is calibrated by comparison to buffers of known pH 4 0 Sample Collection Preservation and Holding Times 4 1 Samples for pH analysis may be collected in either plastic or glass and should be analyzed as soon as possible after collection Analysis on site is preferable to analysis in the lab 5 0 Interferences 5 1Changes in the properties of the electrodes during analysis and chemical effects
116. 20 96 20 96 NA 0 1 mg L total organic carbon TOC 20 96 20 NA 5 mg L dissolved iron Fegiss lt 15 15 96 85 115 5 mg L total iron 15 15 96 85 115 0 007 mg L dissolved iron Mngiss lt 15 lt 15 85 115 0 004 mg L Target reporting limit values for pH and are the minimum difference in readings that can be quantified Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 6 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE 4 Quality Assurance As laboratory analyses are completed the analyst will check data for quality Corrective action will be taken by the analyst whenever the RPD RPE or spike recoveries fall outside of the acceptance range Table 2 Samples from analyses which fail to meet quality criteria will be re analyzed following recalibration of the instrument All data will be entered into computer files and materials related to analyses raw data sheets recorder output computer print outs etc will be kept on file for future reference The Quality Assurance manager Anderson will review laboratory data periodically and will require additional re analysis as warranted 5 Field and Laboratory Equipment Maintenance Regular maintenance of the field and laboratory equipment will be performed following manufacturer guidelines and when the equipment is not meeting manufacturer or laboratory performance specifications 6 Laboratory and Field Equipment Calibration
117. 4 4 EPN 2104 64 5 Ethion 563 12 2 Ethoprop 13194 48 4 Famphur 52 85 7 Fenitrothion 122 14 5 Fensuffothion 115 90 2 Fenthion 55 38 9 Fonophos 944 22 9 Hexamethyl phosphoramide 680 31 9 HMPA Leptophos 21609 90 5 Revision 4 1 53 8141 Page 2 of 16 Malathion 121 75 5 Merphos 150 50 5 Mevinphos 7786 34 7 Monocrotophos 6923 22 4 Naled 300 76 5 Parathion ethyl 56 38 2 Parathion methyl 298 00 0 Phorate 298 02 2 Phosmet 732 11 6 Phosphamidon 13171 21 6 Prothiofos Ronnel 299 84 3 Simazine 122 34 9 Stirophos 22248 79 9 Sulfotepp 3689 24 5 TEPP Terbufos 13071 79 9 Tetrachlorvinphos Tetraethyl pyrophosphate 107 49 3 Thionazin 297 97 2 TOCP Tokuthion 34643 46 4 Triazine Herbicides Trichlorfon 52 68 6 Trichloronate 327 98 0 Tri o cresyl phosphate 78 30 8 Zinophos 2 0 3 0 Note Analytes in parenthesis are not certified by NELAP SUMMARY OF METHOD 21 one liter aliquot of aqueous sample is extracted with methylene chloride by shaking in a separatory funnel The methylene chloride extract is isolated dried and concentrated to a volume of 5mL during a solvent exchange to methyl tert butyl ether MTBE A 15g aliquot of solid or 5g aliquot of sludge sample is mixed with anhydrous sodium sulfate to form a free flowing powder This is solvent extracted three times with 1 1 methylene chloride and acetone using sonication The extract is ready for analysis following solve
118. 4 LCS s is analyzed containing all other NELAP analytes per method per matrix Since historical data is unavailable for these analytes results are simply noted LCS results are compared to the True value Percent Recovery is calculated as indicated in the laboratory Quality Assurance Manual Quality control charts are available in LIMS indicating the percent recoveries mean standard deviation and the upper and lower control limits UCL and LCL Percent recoveries are compared to control limits If the percent recovery for the Laboratory Control Sample does not fall within the acceptance range corrective actions must be taken See SOP Q06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager A method or reagent blank MB or LRB is analyzed with each batch of samples or 1 per 20 samples whichever is more frequent and reported per matrix type 1 2 1 1 Matrix type refers to one of following possible groups water liquid including extracts solid soil sludge or gas If possible it is preferred to group sludge separately from the others solids and CAM TCLP extracts separately from other liquids If the water and liquid procedures are identical one MB may be Revision 7 0 Page 3 of 14 1 2 2 1 2 3 1 2 4 1 2 5 1 2 6 001 performed for both matrices as long as it still represents a frequency of 596 In some cases a meth
119. 5 SOP Definitions 12 0 Safety See SOP 501 Concentrated Acids and Bases SOP 503 Spill Control Policy Revision 5 0 I22 NO2 Page 7 of 6 13 0 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 14 0 Pollution Prevention and Waste Management See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP S07 Pollution Prevention 15 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office 16 0 References Method Source EPA 354 1 Methods for Chemical Analysis of Water and Wastes Standard Methods for the Examination of Water and Wastewater APHA AWWA WEF 18th edition 4500 NO B Note All italicized items are an indication of a variation from the method Approved by Susan K Thomas Date 08 23 06 Revision 4 0 124 DO Page 1 of 6 DISSOLVED OXYGEN STANDARD OPERATING PROCEDURE Edward S Babcock amp Sons AZIDE MODIFICATION D O Probe Standard Methods 4500 O C and G Date Effective 02 01 06 1 Scope and Applications 1 1 This method determines the dissolved oxygen levels in water and wastewater The analysis for DO is a common test for water pollution and for use in waste treatment process control 2 Reporting Limits 2 1 The reporting limit for this method is 0 1 mg L 3
120. 7 Sample filtering will be requested in the notes and needs to be done prior to any analysis of the sample Place a checkmark V next to the note on the Work Order Printout and then follow the appropriate procedure listed below Use the splitter code F on the bottle and Work Order Printout to indicate what has been filtered and preserved It is very important that this information be entered into Element as soon as it has been done or directly Revision 3 0 06 Page 2 of 8 after the splitting process Go to Update Status under comments and enter FILTEREDmmddyyinitials in front of the needs to be filtered note 3 7 For metals filtering Acid rinse filtration apparatus with 1 1 HNO3 Filter sample through a 0 45 micron filter prior to preservation Use a portion of the sample to rinse the filter flask discard this portion and collect the required volume of filtrate A filtered blank must be included with the samples Label blank with date initials along the side of the bottle and list the sample s associated with it Apply the printed label to the samples if it is provided Preserve for metals as per section 6 0 placing a NF on the sample bottle and Work Order Printout 3 7 2 For phosphate or nitrogen filtering Acid rinse filtration apparatus with 1 1 Filter sample through a 0 45 micron filter prior to preservation Use a portion of the sample to rinse the filter flask discard this portion and collect the required volu
121. A pH SM4500 H B 1 pH units 1 14 units 2 point curve total organic nitrogen Org N CALC N A N A N A nitrite nitrogen NO2 N SM4500 NO2 B 1 7 ug L 0 01 1 0 mg L 6 point curve nitrate nitrogen NO3 N EPA 300 0 0 107 mg L 0 1 5 0 mg L 8 point curve ammonia nitrogen NH4 N SM4500 NH3 H 0 06 mg L 0 1 2 0 mg L 6 point curve total phosphorus TP SM4500 P E 0 01 mg L 0 05 1 0 mg L 6 point curve soluble reactive phosphorus SRP ortho P SM4500 P E 0 01 mg L 0 05 1 0 mg L 6 point curve total suspended solids TSS SM2540C 2 8 mg L 5 2000 mg L Standard chemical oxygen demand COD SM5220D 6 5 mg L 10 500 mg L 7 point curve biochemical oxygen demand BOD SM5210B 1 02 mg L Depends on dilution Standards total nitrogen TN CALC N A N A N A total dissolved solids TDS SM2540D 5 5 mg L 10 2000 mg L Standard total Kjeldahl nitrogen TKN EPA 351 2 0 06 mg L 0 1 3 0 mg L 6 point curve E coli SM9221E 1 1 MPN 100 mL 2 1600 MPN 100 mL total arsenic Astotal EPA 200 8 1 6 ug L 5 ug L 2900 ppb 1 point curve total cadmium Catotal EPA 200 8 0 08 ug L 2 ug L 2900 ppb 1 point curve total copper Cutotal EPA 200 8 1 64 ug L 10 ug L 2900 ppb 1 point curve total lead Pbtotal EPA 200 8 0 08 ug L 10 ug L 2900 ppb 1 point curve total zinc Zntotal EPA 200 8 1 4 ug L 10 ug L 2900 ppb 1 point curve total chromium Crtotal EPA 200 8 0 14 ug L 20 ug L 2900 ppb 1 point curve total mercury Hgtotal EPA 200 8 0 03 ug L 0 5 ug L 2900 ppb 1 point curve Varies See o
122. Babcock amp Sons EPA 300 0 Effective Date 02 07 07 TITLE The Determination of Inorganic Anions in Water by Ion Chromatography ANALYTE CAS MCL mg L Chloride Cl 7782 50 5 250 500 600 Nitrate NO 14797 55 8 45 Sulfate SO 14808 79 8 250 500 600 Non NELAP Analytes Fluoride F 7782 41 4 2 0 Nitrite NO 3 29 Phosphate PO Para Chlorobenzene Sulfonic Acid PCBSA 98 66 8 Secondary MCL nonhealth limit recommended upper short term 1 0 Scope and Application 1 1 This method covers the determination of the following inorganic anions RL mg L 1 1 1 Fluoride 0 1 1 1 2 Chloride 1 1 1 3 Nitrate N Nitrate 0 2 1 1 1 4 Nitrite N 0 1 1 1 5 Phosphate P 0 05 1 1 6 Sulfate 0 5 1 1 7 PCBSA 10 1 2 The matrices applicable to each method are shown below Drinking water surface water mixed domestic and industrial wastewaters groundwater reagent waters solids after extraction 11 11 1 3 The working range for these analytes is as follows 1 3 1 Fluoride 0 1 5 mg L 1 3 2 Chloride 1 250 mg L 1 3 3 Nitrate 1 100 mg L 1 3 4 Nitrite N 0 1 5 0 mg L 1 325 Phosphate P 0 05 5 0 mg L 1 3 6 Sulfate 0 5 250 mg L 1 3 7 Perchlorate 1 3 8 PCBSA 0 004 0 25 mg L 1 100 mg L Revision 7 0 119 Anions Page 2 of 15 1 4 This method is recommended for use only by or under the supervision of analysts experienced in the use of ion chromatography and in the interpretation of the resulting ion chromatogra
123. C 8 isobaric elemental correction for tin Revision 3 0 Page 26 of 26 TABLE 8 ACCEPTANCE LIMITS FOR QC CHECK SAMPLE METHOD PERFORMANCE ug L 1 QC Check Sample ELEMENT Aluminum Antimony Arsenic Barium Beryllium Cadmium Chromium Cobalt Copper Lead Manganese Molybdenum Nickel Selenium Silver Thallium Thorium Uranium Vanadium Zinc Standard Average Deviation 2 Conc Recovery 100 100 4 100 99 9 100 101 6 100 99 7 100 105 9 100 100 8 100 102 3 100 97 7 100 100 3 100 104 0 100 98 3 100 101 0 100 100 1 100 103 5 100 101 1 100 98 5 100 101 4 100 102 6 100 100 3 100 105 1 Acceptance Limits 3 S r 92 108 88 112 4 94 108 91 114 90 106 94 107 94 114 90 106 94 108 94 106 86 121 91 111 5 90 107 94 109 94 111 90 110 91 119 Method performance characteristics calculated using regression equations from collaborative study reference 11 Single analyst standard deviation S r Acceptance limits calculated as average recovery 3 standard deviations Acceptance limits centered at 100 recovery Statistics estimated from summary statistics at 48 and 64 ug L Approved by Susann K Thomas Date M12 200 8 09 25 06 Revision 5 0 26 Page 1 of 9 Edward S Babcock amp Sons Standard Operating Procedure SM 5310B Date Effective 09 25 06 TITLE Organic Carbon Total Nonpurgeable and Dissolved Combustion 1 0 Scope and Applica
124. C will report directly to the TASK FORCE TAC and will be responsible for all aspects of the CL nutrient monitoring program including organization and training of field staff scheduling of sampling days data management and quality control and interactions with laboratory personnel associated with the CL nutrient monitoring program Figure 1 Organizational Chart amp Responsibilities Lake Elsinore and Canyon Lake Nutrient TMDL Task Force Component Santa Ana RWQCB TMDL Program Manager Hope Smythe Santa Ana RWQCB Quality Assurance Program Manager TASK FORCE Pavlova Vitale Administrator Mark Norton San Jacinto Watershed TASK FORCE Monitoring Monitoring Program Manager QA Manager Rick Whetsel Lake Elsinore amp Canyon Canyon Lake Monitoring Lake Monitoring Program Manager QA Manager Dr Michael Anderson UCR San Jacinto River Improvement and Protection Program Riverside County was awarded a Proposition 50 Chapter 8 Planning Grant to address illegal dumping in the riparian zones of the dan Jacinto River This program will sponsor trash clean up days fence areas at risk of illegal dumping and acquire properties along the San Jacinto River to restrict access reduce illegal dumping protect riparian habitat and provide buffers from other land uses The SJRIPP will be managed by Alex Gann of Riverside County He will be responsible for coordinating all aspects of the SJRIPP program including organization and training
125. CE TCE MtBE HAAs and THMs are generally not confirmed by reanalysis Results supported by historical data are also generally not reanalyzed but may be qualified N HST Where replicate sample results are available see ESB SOP Q24 for reporting guidance and retest policy 1 5 Surrogates 1 5 1 1 5 2 1 5 3 If the method requires the addition of surrogate a known amount is added to all client and QC samples Surrogate compounds must be added for all organic chromatography methods except when the matrix precludes its use or when surrogate is unavailable Surrogates are also used for Inorganic Chromatography analysis if required by the method Percent Recovery is calculated by computer as indicated in the Quality Assurance Manual Percent recoveries are compared to laboratory acceptance ranges If recoveries do not fall within the control limits see SOP Q06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager Revision 7 0 QOI Page 6 of 14 1 5 4 Quality control charts are available in LIMS indicating the percent recoveries mean standard deviation and the upper and lower control limits UCL and LCL Revision 7 0 Page 7 of 14 001 1 6 Internal Standards 1 6 1 1 6 2 1 6 3 1 6 4 Internal standard calibration is used per method requirements In such cases internal standard is added to all client and QC samples in the
126. CS the meter may need to be recalibrated When the analysis is complete rinse the test bes 3 times with D I water and place test tubes a box so that the water can drain out Leave the pH electrode in storage solution specified by the probe manufacturer 200mL pH 7 buffer with 1g KCl This solution has expiration date of 6 months from date made B sure to cover the filling hol cap when not in use a3 Solid Hazardous waste samples 3 Weigh 10g of sample S032 Add 10ml of D I water to sample 13 XO XO WO the sample more water may be added le with its protective PES If most of the water is absorbed by Additional dilutions are allowed if working with hygroscopic soils or other problematic matrices Document the ratio used on the page 4 Stir periodically for 30 minutes 9 Let settle for one hour 6 Immerse probe into supernate for reading XO XO WO WWW data 9138 7 If sample is a liquid but non aqueous a 1 1 dilution must be used Quality Control Revision 5 0 125 pH Page 5 of 8 Note LO TOs 10 See also ESB SOP Q01 for general QC requirements 1 Duplicates are analyzed at least once with every analytical batch at a minimum of once for every 10 samples per matrix type A maximum difference of 4 0 1 pH units is allowed between sample duplicates 2 Calibration Checks After calibration the pH 4 0 s
127. CTRICAL CONDUCTIVITY Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE Standard Methods 2510 B Date Effective 10 30 06 1 0 Scope and Application Conductivity is the measurement of an aqueous solution s ability to conduct electricity This measurement depends on th presenc of ions their total concentration valence and relative concentrations and the temperature of the solution Conductivity is an indication of salinity of the solution This method is applicable to waters and wastewaters This method may also be used for solid samples if both client and regulator agree to this variation 2 0 Reporting Limit 1 0 wumho cm 3 0 Precision and Bias The RPD of this test is 10 and the relative error 10 in a conductivity range of 147 to 303 umhos cm Standard Methods study Our laboratory s generated data is expected to achieve similar results Refer to Initial Demonstration of Capability Studies and quality control charts maintained in the QA Office 4 0 Working Range 1 0 200 000 umhos ocm 5 0 Summary of Method The resistance to electrical current across a gap in the conductivity cell is measured Conductivity is the reciprocal of the resistance 6 0 Sample Collection Preservation and Holding Times 6 1 The sample may be collected and stored in either plastic or glass 6 2 The sample is refrigerated as soon as possible after collection 6 3 The regulatory hold
128. EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 EPA 8141 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 3L 1L amber glass 1L amber glass 1L amber glass 1L amber lass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber lass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber lass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber lass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber lass 1L amber glass 1L amber glass 1L amber glass 1L amber glass 1L amber glass Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Unpreserved Page 27 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 28 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE
129. Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A7 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA To determine the overall quality of data the results of quality control sample analysis will be evaluated in terms of the precision accuracy recovery and completeness data quality objectives established for this program Results falling outside of recommended control limits will trigger correction action including recalibration and reanalysis of suspect samples Precision Precision is the reproducibility of measurements under a given set of conditions For large data sets precision is expressed as the variability of a group of measurements compared to their average value i e standard deviation For duplicate or replicate measurements precision is expressed as the relative percent difference RPD of a data pair Field Precision For Lake Elsinore field precision will be assessed through the collection and analysis of field triplicate samples to be collected three times per year A control limit of less than 25 percent will be used for relative difference Laboratory Precision Analytical laboratory precision will be evaluated by analysis of replicate samples Duplicates will be analyzed at a frequency of no less than one per 10 samples The RPD between the duplicates will be calculated as follows RPD Cy C2 C1 C2 2 100 Where C and are concentrations of analyte in replicate samples 1 and 2 a control limit of
130. Helpful Hints Do not remove the lids from the DO bottles prior to analysis Keep the lids on the bottles at all times when not being used 7 Safety Issues Prepared sample is corrosive Wear gloves and safety goggles when performing this analysis 7 1 See SOP S01 Concentrated Acids and Bases SOP S03 Spill Control Policy 8 Instrumentation Equipment 8 1 4 25mL burets one each for manganese sulfate solution alkali iodide azide solution sulfuric acid solution and sodium thiosulfate titrant for use in Winkler titration azide modification 8 2 300 ml DO bottles 8 3 Dissolved Oxygen meter YSI Model 5000 Allow 30 minutes to warm up or leave instrument on 8 4 Dissolved Oxygen probe YSI 5010 Store probe in BOD bottle filled with about inch of D water 9 Reagents and Standards 9 1 Manganous Sulfate solution Dissolve 400 g MnSO4 2H50 or 364 g 504 0 in 1 liter of Nanopure water Store at room temperature for up to six months 9 2 Alkali Iodide Azide reagent Dissolve 500 g NaOH in Nanopure water Allow to cool Add 150g KI and dissolve Dilute to 1 liter Dissolve 10 0 g NaN3 into 40 mL of Nanopure water Add to 40 mL to IL mix Store at room temperature for up to six months 9 3 Starch solution Dissolve 20 g soluble starch and 2 g C7HgO3 Revision 4 0 124 DO Page 3 of 6 10 9 4 Salicylic Acid in 1 liter of heated Nanopure water or purchase 1 starch indicator 9 5 Concent
131. JRWC for the purposes of their Prop 50 Chapter 8 grant samples delivered to contract laboratories for analysis will include a Chain of Custody form The contracting Laboratory will generate records for sample receipt and storage analyses and reporting LESJWA has an existing database of laboratory and field measurement data from previous studies This database along with all future data will be maintained by LESJWA under the direction of the Monitoring Program Manager Beginning in June 2007 all laboratory and field measurement data submitted to LESJWA for inclusion in the SAWDMS database will follow the guidelines and formats established by SWAMP http www waterboards ca gov swamp qapp html All chemical monitoring records generated by these programs will be stored at SAWPA The contract laboratory s records pertinent to the program will be maintained at the contract laboratory s main office Copies of all records held by the contract laboratory will be provided to the TASK FORCE and stored in the TASK FORCE archives Copies of this QAPP will be distributed to all parties involved with the project including field collectors and the TASK FORCE in house laboratory analyst Copies will be sent to each Contract Laboratory Quality Assurance Manager for distribution to appropriate laboratory staff Any future amended QAPPs will be held and distributed in the same fashion originals of this first and subsequent amended QAPPs will
132. L 5 7 point curve Ethion OP EPA 8141 0 56 ug L 4 50 ug L 5 7 point curve Ethoprop OP EPA 8141 1 ug L 4 50 ug L 5 7 point curve Famphur OP EPA 8141 0 68 ug L 4 50 ug L 5 7 point curve Fenitrothion OP EPA 8141 0 74 ug L 4 50 ug L 5 7 point curve Fensulfothion OP EPA 8141 0 68 ug L 4 50 ug L 5 7 point curve Fonophos OP EPA 8141 0 75 ug L 4 50 ug L 5 7 point curve Fenthion OP EPA 8141 0 66 ug L 4 50 ug L 5 7 point curve Leptophos OP EPA 8141 0 48 ug L 4 50 ug L 5 7 point curve Malathion OP EPA 8141 0 8 ug L 4 50 ug L 5 7 point curve Lake Elsinore amp Canyon Lake Nutrient TMDL Page 34 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Merphos OP EPA 8141 1 8 ug L 4 50 ug L 5 7 point curve Mevinphos OP EPA 8141 1 1 ug L 4 50 ug L 5 7 point curve Monocrotophos OP EPA 8141 0 78 ug L 4 50 ug L 5 7 point curve Naled OP EPA 8141 0 55 ug L 4 50 ug L 5 7 point curve Parathion ethyl OP EPA 8141 0 63 ug L 4 50 ug L 5 7 point curve Parathion methyl OP EPA 8141 0 61 ug L 4 50 ug L 5 7 point curve Phorate OP EPA 8141 0 93 ug L 4 50 ug L 5 7 point curve Phosmet OP EPA 8141 0 65 ug L 4 50 ug L 5 7 point curve Phosphamidon OP EPA 8141 0 44 ug L 4 50 ug L 5 7 point curve Ronnel OP EPA 8141 0 49 ug L 4 50 ug L 5 7 point curve Stirophos Tetrachlorovinphos OP EPA 8141 0 58 ug L 4 50 ug L 5 7 point curve Sulfotepp OP EPA 8141 0 87 ug L 4 5
133. L Margin of Safety when reporting loads for compliance The data will be used within the context of the SWAMP umbrella and the SWAMP database to determine whether Lake Elsinore and or Canyon Lake should be delisted Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 41 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE 1 REFERENCES APHA 1998 Standard Methods for the Examination of Water and Wastewater 20 Edition American Public Health Association Washington DC Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 42 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 43 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE ATTACHMENT 1 EXAMPLE SAN JACINTO STORM EVENT FIELD DATA SHEET FORM Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 44 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 45 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE San Jacinto River Watershed TMDL Field Data Sheet Station ID No Station Name SAMPLE Time 24 hr clock Date Number of containers Staff Gauge Depth Meter Depth Lab No Water Temp pH Cond Observations SAMPLE Time 24 hr clock Date Number of containers Staff Gauge Depth Meter Depth Lab No Water Temp pH Cond Observations SAMPLE Time 24 hr clock Date Number of
134. LCS source to verify the curve Results must be within 90 110 of the expected value or a new curve may be necessary 11 6 Continuing Calibration Verification Checks The calibration is verified on a daily basis by analysis of the 0 25 mg L Calibration Check analyzed at the end of the day s batch Recovery must be within 85 115 of expected value 12 0 Procedure for Ortho Phosphorus 12 1 Pour up to 10mL of sample into beaker Adjust the pH of the sample prior to measurement if it is suspected to be 6 5 or gt 8 5 The sample must be clear Filter through 0 45micron disk filter if Revision 5 0 I27 OP Page 8 of 9 necessary If the filtrate is still turbid or discolored read the background As Ol gL Zero the spec to a blank prior to addition of reagents Read the sample prior to addition of reagents This absorbance is subtracted from the reading acquired in section 12 5 Lana If using less than 10mL of sample bring up the volume to 10ml with nanopure water Record the volume of sample used 122 3 Spike 10uL of LCS Intermediate into the lab control matrix spike and matrix spike duplicate 12 4 Add 1 6mL of P Reagent to all samples 1245 Swirl samples then let them stand at least 10 minutes but not more than 30 minutes 12 6 Read the absorbance of the samples in the spectrophotometer at 880 nm
135. LFB Historical recovery is examined on a yearly basis and is available in the LIMS 9 3 6 Instrument performance CCB CCV For all determinations the laboratory checks instrument performance and verifies that the instrument is properly calibrated on a continuing basis To verify calibration run the calibration blank and calibration standards immediately following each calibration routine after every ten analyses and at the end of the sample run The results of the analyses of the standards will indicate whether the calibration remains valid All metals in the calibration blank must be less but not more negative than 2 the reporting limit The analysis of all analytes within the standard solutions must be within 10 of calibration If the calibration cannot be verified within the specified limits the instrument must be recalibrated The instrument responses from the last working calibration check may be used for recalibration purposes however it must be verified before continuing sample analysis by an acceptable reprocessed CCV and CCB If the continuing calibration check is not confirmed within 15 the previous ten samples must be reanalyzed after recalibration Therefore 10 is considered the recalibration limit and 15 is considered the re Revision 3 0 M12 200 8 Page 14 of 26 analysis limit If the sample matrix is responsible for the calibration drift it is recommended that the previous ten samples be reanalyzed in gr
136. LOD Verification a yearly basis a QC sample is spiked at a level of 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL 8 Constant Weight Study On an annual basis a constant weight study is performed 200mg of calcium sulfate is placed in three TDR dishes by filtering a 100mL aliquot of a 2000mg L solution This hydroscopic salt is intended to represent the Revision 5 0 I29 TDS Page 8 of 8 most challenging sample Dishes are placed in the oven for one hour cooled and weighed Dishes are placed back in the oven for 15 minutes cooled and then weighed This process is repeated until the weights are constant Constant weight is defined as weight change less than 4 of the previous weight or a change less than 0 5mg whichever is less The constant weight determined by this study will be used as the drying time for the procedure Empty dishes are also tested to determine the necessary dish preparation time 14 0 Corrective Action For Out of Control or Unacceptable Data See SOP Q06 Corrective Action 15 0 Pollution Prevention and Waste Management See SOP S07 Pollution Prevention 16 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office 17 0 References 17 1 St
137. Mout NRPDo NMoRo or NRPDa to the sample If sample is unavailable for follow up or past the holding time attach the appropriate qualifiers to the QC QMout QRPDo QRPDa QMoRo and QFnes or QFhte and to the sample NMout NRPDo NMoRo NRPDa If due to the nature of the analysis the follow up is not performed during the initial run 3 9 1 Enter the original data for the sample and QC and attach the qualifier SUS to the sample used for the MS or DUP QRPDo QMoRo or QMout and QFinP to the MS or DUP 3 0 2 Create a re extract for that sample Explain in Comments that a re extract was created for QC follow up purposes Create a separate batch for the re extract sample and the MS or DUP 3 9 3 Enter the data from the re analyzed QC and sample with the new batch If the follow up QC still does not pass MS MSD or duplicate criteria attach the proper qualifier to the QC QFini and one of the following QMint QMout QMSD QRPDo QRPDa QRPDI and to the sample NMout NRPDo NMoRo or NRPDa 3 9 4 The SUS and QFinP qualifiers must be removed from the original data Tag the original QC with QFpas or QFini The original sample result must be tagged with NMout NRPDo NMoRo or NRPDoa if the follow up did not correct the problem 3 10 If sample matrix is considered to be the cause of the QC failure attach QMint to the QC and NMint to the sample The analyst must however have valid reasons to suspect matrix For example a MS
138. N Compound Low Medium High Azinphos methyl 156 1104 6 87 Bolstar 102 1034715 79 Chlorpyrifos NR 66 17 79 Coumaphos 93 89 11 90 Demeton 169 64 6 75 Diazinon 87 96 3 75 Dichlorvos 84 39 21 71 Dimethoate NR 48 4 7 98 Disulfoton 78 78 6 76 EPN 114 93 4 8 82 Ethoprop 65 70 7 75 Fensulfonthion 72 814 18 111 Fenthion NR 434 7 89 Malathion 100 814 8 8l Merphos 62 53 60 Mevinphos NR 71 63 Monocrotophos NR NR NR Naled NR 48 NR Parathion ethyl 75 80 8 80 Parathion methyl NR 41 4 3 28 Phorate 75 77 6 78 Ronnel NR 83 12 79 Sulfotep 67 72 8 78 TEPP 36 34 33 63 Tetrachlorvinphos 50 814 7 83 Tokuthion NR 404 6 89 Trichloroate 56 53 53 NR Not recovered Revision 4 0 O54 8081 Page 1 of 16 Standard Operating Procedure Edward S Babcock amp Sons Date Effective 04 15 06 METHOD 8081A TITLE ORGANOCHLORINE PESTICIDES BY GAS CHROMATOGRAPHY INSTRUMENTATION Gas Chromatography 1 0 SCOPE AND APPLICATION 1 1 Method 8081 is used to determine the concentrations of various organochlorine pesticides in extracts from solid and liquid matrices using fused silica open tubular capillary columns with electron capture detectors ECD The compounds listed below are determined by a dual column analysis system Analytes in parenthesis are not certified by NELAP 1 2 Aqueous Range Single peak pesticides 0 01ppb 5ppb Chlordane Toxaphene 0 1 1ppb 40ppb Nonaqueous Range Solid single
139. QUALITY ASSURANCE PROJECT PLAN FOR LAKE ELSINORE CANYON LAKE AND SAN JACINTO RIVER TMDL WATERSHED MONITORING SAN JACINTO WATERSHED COMPONENT OF THE SANTA ANA INTEGRATED WATERSHED PLAN AND SAN JACINTO RIVER IMPROVEMENT AND PROTECTION PROGRAMS April 2007 Organization Implementing the Monitoring Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE San Jacinto River Watershed Council and Riverside County Prepared by Lake Elsinore amp San Jacinto Watersheds Authority Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 2 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE 1 APPROVAL SIGNATURES Mark Norton TASK FORCE Administrator Signature Hope Smythe TMDL Program Manager Signature Pavlova Vitale Quality Assurance Program Manager Signature Pat Boldt Quality Assurance Program Manager Signature Alex Gann Quality Assurance Program Manager Signature David Woelfel Grant Manager SJRIPP Signature Steve Clark Quality Assurance Manager Watershed Monitoring Program Signature Sarah Garber Quality Assurance Manager Lake Elsinore amp Canyon Lake Monitoring Program Signature Lake Elsinore amp Canyon Lake Nutrient TMDL Task Force Date Santa Ana Regional Water Quality Control Board Date Santa Ana Regional Water Quality Control Board Date San Jacinto River Watershed Council Date Riverside County Date Santa
140. RGP Total Phosphorus minus phosphorus generated from digest SM 4500 P B 2 below 13 2 4 Acid Hydrolyzable Phosphorus PAHYDRO see Standard Methods 4500 P B 2 Phosphorus resulting from this digest minus ortho phosphate acid hydrolysable phosphorus Revision 5 0 I42 TP Page 11 of10 13 22 25 Total Phosphate PO4 Total Phosphorus x3 14 0 Definitions See SOP Q15 SOP Definitions 15 0 Corrective Action For Out of Control Or Unacceptable Data 15 1 See SOP Q06 Corrective Action 16 0 Pollution Prevention and Waste Management 16 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Waste 2 SOP S06 Disposal of Chlorinated Solvents 3 SOP S07 Pollution Prevention 4 Wastes are dumped in the High Acid Concentration Waste barrel 16 16 16 17 0 Method Performance Text Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office References Standard Methods for the Examination of Water and Wastewater AWWA APHA WEF 18 Edition 4500 P B E Methods of Chemical Analysis of Water and Wastes EPA Method 365 2 Note All italicized items are an indication of a variation from the method Approved by Susan K Thomas Date 08 23 06 Revision 5 0 145 KJN Page 1 of 10 AUTOMATED KJELDAHL NITROGEN Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE EPA Method 351 2 Effect
141. Relative standard deviation between the four replicates must be less than or equal to 20 9 4 Performance Evaluation Studies are performed twice a year This is accomplished by obtaining a QCS sample from an outside source and evaluating it s performance based on study acceptance criteria 9 5 Assessing Laboratory Performance mandatory 9 5 1 Laboratory reagent blank LRB or Method Blank MB The laboratory must analyze at least one LRB with each batch of 20 or Revision 4 1 Page 11 of 21 9 5 2 9 5 3 M07 200 7 fewer samples of the same matrix LRB data are used to assess contamination from the laboratory environment For batch acceptance values must be lt the reporting limit If one half the reporting limit is less than the MDL LRB values must be the MDL for those analytes If the LRB is unacceptable fresh aliquots of the samples must be prepared and analyzed again for the affected analytes after the source of contamination has been corrected and acceptable LRB values have been obtained Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured raw concentration of the sample Blank results below the 2 the reporting limit or below the MDL are considered to be ND and will not require a note Laboratory fortified blank LFB or Blank Spike BS The laboratory analyzes at least one LFB with each batch of sa
142. SAMPLING FIELD LOG FORM Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 48 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Page 49 LAKE MONITORING PROJECT FIELD LOG U C H Date Personnel Weather Conditions Time Depth Temp pH DO EC mS cm Chl a Turb Secchi Site mg L NTU Depth cm ay eC g ug L Signature Date Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 50 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 51 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE ATTACHMENT 3 EXAMPLE CHAIN OF CUSTODY FORM Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 52 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL Page 53 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE E S Babcock amp Sons Inc Fels one eter eee Chain of Custody amp Sample Information Record 909 653 3351 FAX 909 653 1662 Client Contact Phone No Rushes Project Name Turn Around Time Routine 3 5 Days 48 Hours 24 Hours Require Approval Aaditional Charges Project Location May Apply Sampler Information amp Preser
143. The control is a standard from a noncalibration source that is processed in the same manner as a sample and is used to determine batch acceptance 1 1 1 1 Matrix type refers to one of following possible groups water liquid including extracts solid soil sludge or gas If possible it is preferred to group sludge separately from the others solids and CAM TCLP extracts separately from other liquids If the water and liquid procedures are identical one LCS may be performed for both matrices as long as it still represents a frequency of 5 1 1 2 For specific analyses it may be impractical to perform a LCS i e settleable solids dissolved oxygen sulfide etc See method SOPs for specifics 1 1 3 The laboratory fortifies LCS samples with all reportable components with the following exceptions Revision 7 0 Page 2 of 14 1 1 4 1 1 5 1 2 Blanks 1 2 1 01 1 1 3 1 The method specifies specific spiking components 1 1 3 2 Components that interfere with each other may be excluded or handled separately 1 1 3 3 Test methods with a long list of target analytes will spike only a core group of compounds This core group of spiking compounds represents all chemistries elution patterns and masses The core group must consist of the following number of spiking compounds of target analytes of spiking compounds in LCS mix 1 10 100 11 20 80 at least 10 compounds gt 20 16 compounds 1 1 34 Every two years a set of
144. Total sulfide bottles ZNAC 16 0 Sample Storage 16 1 Metal sample bottles are stored on the Bakers carts in the metals laboratory 16 2 The inorganic unpreserved carts are on the east wall of the walk in refrigerator 16 3 Along the west wall of the walk in refrigerator are the following carts from left to right hydrocarbons other organics haz mat oil and grease NO3 cyanide and phenol sulfuric preserved and COT only carts 16 4 Organics 16 4 1 refrigerator 1 wastewater VOA wastewater TOX TOC soils solids sludges 16 4 2 refrigerator 6 other samples possibly contaminated that cannot be in any other refrigerator 16 4 3 refrigerator 7 drinking water VOA s 531 1 547 and TOX 16 5 Soils agricultural are placed in the rolling and sieve area next to the soils drying oven 16 6 Bacti analyzed immediately or stored in the walk in on the Bacti cart 16 7 Extracts Revision 3 0 06 Page 7 of 8 16 7 1 TCLP and CAM extracts stored in the walk in on the standards cart 16 7 2 Water extracts usually made and used within 24 hours however if the analysis has a longer holding time the extract is stored in the walk in refrigerator 16 7 3 Soil ag extracts BEX and WEX if not analyzed immediately are placed in the walk in refrigerator for a maximum of 48 hours AEX and SEX stored on the metals lab bench prior to analysis Extracts are not stored after analysis 16 7 4 Organic extracts
145. Working Range 3 1 The working range starts at 0 1 mg L and continues to the saturation point about 8 9 mg L at STP 4 Summary of Method 4 The azide modification is one example of the iodometric test which is a commonly used titrimetric procedure It is based on the addition of divalent manganese solution which in the presence of a strong alkali forms manganese hydroxide DO rapidly oxidizes an equivalent amount of manganese hydroxide to a higher valency state In the presence of acid an equivalent amount of iodide in the solution is liberated as iodine The iodine is titrated with sodium thiosulfate 4 2 The oxygen membrane electrode measures the diffusion current caused by oxygen traveling across a semipermeable membrane 5 Sample Collection Preservation and Holding Times 5 1 The sample is collected in a 300 mL glass bottle Analyze as quickly as possible if using probe method For Winkler method the sample may be set in the field and analyzed within 8 hours See sections 11 1 1 through 11 1 7 for procedure Revision 4 0 124 DO Page 2 of 6 6 Interferences 6 1 The azide modification Oxidizing or reducing materials and iron levels of over 1 mg L can cause interferences 6 2 Membrane electrode Membrane electrodes are very sensitive to changes in temperature Prolonged use of the electrode containing other gasses that will permeate the membrane such as hydrogen sulfide will decrease cell sensitivity 6 3
146. a sample or a dilution of sample with the final volume of 10ml and digest 9 8 Calibration Standards for Curve 9 8 1Stock KHPO previously dried in a 105 C oven and stored in a desiccator 9 8 21Intermediate 1000ppm Weigh up 4 394g KH PO into 1L of Nanopure Keep at room temperature This standard may be kept for up to 12 months or replaced sooner if comparison with QC samples indicate a problem 9 8 3 Working Standards Revision 5 0 T42 TP Page 6 of10 9 8 3 1 Pipette 1ml of 1000ppm PO4 P Intermediate standard into 1 L of nanopure water 9 8 3 2 a year or when calibration checks indicate a need digest various amounts of above solution to create a six point curve Solutions are made fresh each time 10 0 Procedure for Total Phosphorus 10 1 Digestion 10 1 1 Acid rinse all glassware Use 100ml beakers for digestion 10 1 2 Transfer 10ml of well mixed sample preserved with Sulfuric acid into each beaker 10 1 3 Spike 50ul of 100ppm Stock standard into 10ml nanopure water for the lab control matrix Spike and matrix spike duplicate T 1 24 Add lmi of Nitric Acid conc to each beaker 10 1 5 Add 1 1 of Sulfuric Acid Mixture to each beaker 10 1 6 Digest on edge of hot plate setting 4 6 to Sulfuric Acid white fumes Allow water and Nitric acid to steam off Once there appears to be a thin coating of H2SO4 fumes in
147. acceptance range of 80 to 120 recovery the analysis is stopped until the cause is determined and the LCS is in control 8 3 Matrix Spikes and Matrix spike duplicates 8 3 1 Spiking solution Pipette 0 2mL of stock LCS on top of sample prior to digestion for MS and MSD The spike concentration is 1 mg L ammonia nitrogen in solution 8 4 Calibration Standard 8 4 1 8 4 2 8 4 3 8 4 4 Stock Ammonium chloride NHACI Intermediate Standard 1000ppm 8 4 2 1 Dehydrate Ammonium chloride NHA4CI in a 105 C oven Allow to cool in a dessicator 8 4 2 2 Weigh out 3 819 g Ammonium Chloride Dilute to 1 liter with D I water in a volumetric flask 8 4 2 3 Pour the solution into a 1 liter amber bottle Keep out of sunlight Solution is stored at room temperature for up to one year Standards can be replaced sooner if comparison with QC samples indicate a problem Intermediate Standard A 50ppm Dilute 1 0mL of above intermediate standard 8 4 2 up to 20mL with digested digestion reagent This solution is prepared fresh Working Calibration Standards Fresh solutions are made each time a calibration is performed A 3ppm standard is diluted by adding making 600 uL of 50ppm Intermediate standard up to 10 mL with digested digestion reagent The other standards are diluted from the 3ppm standard by the instrument with digested digestion reagent Working Calibration standards concentrations are 3 0 2 0 0 99 0 51 0 24 and 0 09
148. ach analyte the mean recovery value of four of these samples must fall in the proper acceptance range For aqueous samples 70 13096 with a RSD 2096 For poorly performing analytes the criteria from Table 6 of EPA Method 8141B Rev 2 is utilized For analytes not found in Table 6 the range is set to equal that of a similar poor performing analyte For nonaqueous samples 70 13096 with a RSD 2096 For poorly performing analytes the criteria from Table 7 of EPA Method 8141B Rev 2 is utilized For analytes not found in Table 7 the range is set to equal that of a similar poor performing analyte Since our data is compared to performance data developed from single laboratory data certain analytes may be outside the limits however the majority should be within the acceptance limits per 8000B sec 8 4 7 Demonstration of Continuing Proficiency On an annual basis analysts must turn in valid LCS data from four consecutive LCS samples results from a successful Performance Evaluation Study or a valid cell change form See ESP SOP Q01 If four consecutive LCS samples are used percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 40 Performance Evaluation Studies are performed twice a year Revision 4 1 53 8141 Page 13 of 16 11 0 PROCEDURE 11 1 Extraction See SOP O05 O03 and O51 11 2 Gas Chromatography 11 2 1 Sect
149. ach analytical run If the Low Level CCV varies by more than 15 samples having results less than 35ppm are reanalyzed 9 5 3 2 RL Check Standard 1 A standard at the reporting limit is analyzed This is used to validate samples reported as ND and to evaluate instrument sensitivity should calibration checks show a low bias The standard should have a signal greater than the method blank 9 5 4 Calibration Standards Cl NO3 SO4 The eight standards below made from a 1000ppm stock solution into a volumetric flask or a graduated cylinder and brought up to volume with Nanopure water Std 1 mL into 1L Std 5 mL into 200mL Cl 1 ppm 1 0 Cl 50 10 1 ppm 1 0 NO 50 10 SO 0 5ppm 0 5 SO 50ppm 10 Std 2 mL into 50mL Std 6 mL into 50mL Cl 10ppm 0 5 Cl 75ppm 3 75 10ppm 0 5 NO 60ppm 3 0 SO 10ppm 0 5 SO 100ppm 5 0 Std 3 mL into 50mL Std 7 mL into 50mL Cl 20ppm 1 0 Cl 100ppm 5 0 NO 20ppm 1 0 NO 75ppm 3 75 SO 20ppm 1 0 SO 150ppm duo Std 4 mL into 50mL Std 8 mL into 200mL Cl 35ppm 1 75 Cl 250ppm 50 NO 35ppm 175 NO 100 20 SO 35ppm 1 75 SO 250ppm 50 Revision 7 0 119 Anions Page 8 of 15 9 5 5 PCBSA Calibration Standards 9 5 5 1 Stock Standard Salt 4 Chlorobenzenesulfonic acid purchased from a certified vendor Store at room temperature for up to 10 years from date received 9 5 5 2 Intermediate Standard 100ppm Weigh 0 1g of 4 Chlorobenzenesulfonic acid into 1L of Nanopure 9 5 5 3 Work
150. afety Training provided by an appropriately qualified trainer and or contractor of the Health and Safety branch of the State and or equivalent university training The training will cover the general health and safety issues associated with fieldwork including sampling The monitoring manager will provide specific training pertinent to the details of a particular sampling program This training will include but not be limited to proper use of field equipment health and safety protocols sample handling protocols and chain of custody protocols Field staff training is documented and filed at LESJWA s headquarters SAWPA Documentation consists of a record of the training date instructor whether initial or refresher and whether the course was completed satisfactorily All commercial laboratories contracting with the TASK FORCE or SJRIPP will provide training to its staff as part of its SOP All contracting laboratories will maintain their own records of its training Those records can be obtained if needed from the contract laboratory through their Quality Assurance Officer Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 22 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A9 DOCUMENTATION AND RECORDS The TASK FORCE and SJRIPP will maintain a record of all field analyses and samples collected for their respective projects The TASK FORCE will maintain field analyses and sample records on behalf of itself and the S
151. ake Nutrient TMDL QAPP Page 29 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Table 9 Lake Elsinore and Canyon Lake Sampling Methods Samia Maximum Paramietei Sampling Va Containers Preservation chemical Holding Time SOP size type temperature light Preparation ml analysis Field Analyses dissolved oxygen DO In situ N A N A Measure on site N A water temperature In situ N A N A Measure on site N A specific conductance In situ N A N A Measure on site N A pH In situ N A N A Measure on site N A turbidity In situ N A N A Measure on site N A water clarity secchi depth In situ N A N A Measure on site N A oxidation reduction potential In situ N A N A Measure on site N A chlorophyll a In situ N A N A Measure on site N A Laboratory Analyses RR 5 lt 4 C field Filter HxSO ammonia nitrogen NH4 N 1060 B 125 Plastic to pH 2 lab 28 days nitrate nitrite nitrogen NOs NO gt N 1060 125 Plastic e ied E iad to 28 days total nitrogen TN 1060 B 125 Plastic lt 4 C 28 days lt 4 C field Filter H250 soluble reactive phosphorus SRP 1060 B 125 Plastic to pH 2 lab 28 days total suspended solids TSS 1060 B 500 Plastic 4 C 7d biochemical oxygen demand BOD 1060 B 1000 Plastic 4 6h chemical oxygen demand COD 1060 B 1000 Plastic 4 28 d total phosphorus TP 1060 B 125 Plastic 4 C or H2SO to pH
152. an that used for instrument calibration 50ppb 1ppb Hg An independent standard is defined as a standard composed of the analytes from a source different from those used in the standards for instrument calibration The QCS ICV is not processed This solution is made every 48 hours or daily for Hg and Ag Refer to the standard preparation logbook for details of the preparation dilutions Laboratory Fortified Blank LFB or LCS or BS and Laboratory Fortified Matrix LFB or MS To an aliquot of LRB add aliquots from noncalibration multielement stock standards The fortified concentration range for drinking waters is 25 ug L except for mercury which is 2 5 ug L for wastewater 200 ug L Hg 4 ug L The LFB and MS MSD are carried through the entire sample preparation scheme as the samples including sample digestion when applicable Add internal standards to this solution after preparation has been completed This solution is made fresh daily Refer to the standard preparation logbook for details of the preparation dilutions 7 10 Autolens Solution See standard log for preparation 8 SAMPLE COLLECTION PRESERVATION AND STORAGE 8 1 8 2 8 3 Prior to sample collection of an aqueous sample consideration is given to the type of data required i e dissolved or total recoverable so that appropriate preservation and pretreatment steps can be taken The pH of all aqueous samples is tested after sample receipt to ensure the sample h
153. analyzed one per batch or for every 20 samples per matrix type whichever is greater LOTZE If the matrix spike and matrix spike duplicate is not within the control limits of 80 120 maximum RPD of 20 the spikes should be re analyzed If the results are the same the sample used as the spike must be qualified 10 3 Method Blank 10 3 1 One method blank per batch of 20 samples is analyzed using 10mL of Nanopure water The blank must be below the reporting limit but not more negative than the RL for batch acceptance Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a note T0 35 2 If the instrument is zeroed to a blank a method blank is not required 10 4 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit 10 4 1 LOD Verification On a yearly basis a vial of reagent water is spiked at a level of at least 2 3 times analyte MDL The sample is analyzed Analyte
154. ance cellulose fibers 3 1 5 soluble or insoluble carbonaceous materials adsorbed or entrapped on insoluble inorganic suspended matter for instance oily matter adsorbed on silt particles Note IC interference can be eliminated by acidifying samples to pH 2 or less to convert IC species to CO Subsequently purging the sample with a purified gas removes the CO by volatilization Sample purging also removes POC so that the organic carbon measurement made after eliminating IC interferences is actually a NPOC determination determine VOC to measure true TOC In many surface and ground waters the VOC contribution to TOC is negligible Therefore in practice the NPOC determination is substituted for TOC Revision 5 0 26 Page 2 of 9 4 0 5 0 6 0 3 2 Method Definitions 5 1 3 2 1 Inorganic Carbon IC carbonate bicarbonate dissolced carbon dioxide 3 2 2 Total Organic Carbon TOC all carbon atoms covalently bonded in organic molecules 3 2 3 Dissolved Organic Carbon DOC the fraction of TOC that passes through a 0 45micron filter 3 2 4 Particulate Organic Carbon POC or nondissolved organic carbon the fraction of TOC that remains on a 0 45micron filter 3 2 5 Volatile Organic Carbon VOC or purgeable organic carbon the fraction of TOC removed by purging 3 2 6 Nonpurgeable Organic Carbon NPOC the fraction of TOC not removed by purging Environmental Relevance The final usefulness of the carbon measu
155. and COD pH biochemical oxygen demand BOD dissolved oxygen DO turbidity total organic nitrogen water clarity secchi depth dissolved organic nitrogen total dissolved solids TDS nitrite nitrogen nitrate nitrogen NOs N NO3 N chlorophyll a ammonia nitrogen NH N oxidation reduction potential total nitrogen TN total hardness total inorganic nitrogen TIN dissolved manganese total phosphorus TP dissolved iron Fegiss soluble reactive phosphorus SRP ortho P total organic carbon TOC total organic phosphorus dissolved organic carbon DOC dissolved organic phosphorus Figure 6 Sampling Sites on Canyon Lake water quality and related data collected through these programs will be submitted to the Santa Ana Regional Board annually over the life of the program Data will be submitted in the form of an annual monitoring report each year no later than August 15 beginning with 2006 At the end of the program the TASK FORCE will provide a full listing and summary of the data collected including a trend analysis using all data collected These data will also be summarized and reported in the San Jacinto River Watershed Council s San Jacinto Component of the Santa Ana Integrated Watershed Plan interim and final grant progress reports The final grant progress report is due by January 2008 Lake Elsinore amp C
156. and document for each wavelength the effect from the known interferences given in Table 2 and to check for the presence of interferents in samples and utilizing a computerized correction routine To determine the appropriate location for off line background correction the analyst scans the area on either side adjacent to the wavelength and records the apparent emission intensity from all other method analytes This spectral information is documented and kept on file The location selected for background correction is free of off line interelement spectral interference If a wavelength other than the recommended wavelength is used the analyst determines and documents both the on line and off line spectral interference effect from all method analytes and provide for their automatic correction on all analyses Tests to determine the spectral interference are done using analyte concentrations that will adequately describe the interference 4 2 Physical interferences are effects associated with the sample nebulization and 4 3 transport processes Changes in viscosity and surface tension can cause significant inaccuracies especially in samples containing high dissolved solids or high acid concentrations If physical interferences are present they are reduced by using a peristaltic pump and an internal standard Additionally the analyst may utilize such means as diluting the sample if the recovery on the internal standard is low Another problem that
157. and requires less frequent replacement of tanks than compressed argon in conventional cylinders Revision 4 1 MO7 200 7 Page 6 of 21 6 2 6 3 6 4 6 1 3 variable speed peristaltic pump is required to deliver both standard and sample solutions to the nebulizer 6 1 4 optional Mass flow controllers to regulate the argon flow rates especially the aerosol transport gas are highly recommended Their use will provide more exacting control of reproducible plasma conditions Autopipetters Labware A clean laboratory work area designated for trace element sample handling must be used Sample containers can introduce positive and negative errors in the determination of trace elements by contributing contaminants through surface desorption or leaching depleting element concentrations through adsorption processes All reusable labware glass quartz polyethylene PTFE FEP etc is sufficiently cleaned for the task objectives Plastic volumetric flasks are rinsed with 1 1 nitirc and Nanopure water See preparation SOP for washing instructions of digestion glassware 6 3 1 Glassware Volumetric flasks graduated cylinders funnels and centrifuge tubes metal free plastic 6 3 2 Assorted calibrated autopipettes 6 3 3 Microwave cylinders with Teflon sleeves 6 3 4 15 dram snap cap vials 6 3 5 Plastic autosampler tubes 6 3 6 One piece stem FEP wash bottle with screw closure 125 mL capacity Plastic sample bottles New bottles are u
158. and should be checked for the presence of impurities prior to mixing with the other elements Solutions are stored at room temperature Manufacturer specified holding times are observed Preparation of calibration standards Fresh multielement calibration standards are prepared every 48 hours or daily for Hg and Ag Mixed calibration standard solutions are prepared by diluting the stock standard solutions to levels in the linear range for the instrument in a solution consisting of 2 percent v v HNO3 and 1 percent v v HCl in reagent water The calibration standard is 10 ppb for all metals of interest except Hg which is at 0 5ppb Two linearity check standards are also analyzed one at 100 ppb with Hg at 2ppb and the second at 500ppb containing no Hg Refer to the standard preparation log book for details of the preparation dilutions Internal Standards Stock Solution Scandium indium terbium and germanium stock standards solutions are purchased at a concentration of 1000 ug ml from a reputable commercial vender See standard prep log for dilution details AII standards blanks and samples contain each internal standard at 50 and or 16 7ug L NOTE If mercury is to be determined by the direct analysis procedure add an aliquot of the gold stock standard 1000 mg L in 5 to the internal standard solution sufficient to provide a concentration of 500 ug L in final the dilution of all blanks calibration standards and samples Bl
159. andard Methods for the Examination of Water and Wastewater AWWA APHA WEF 18th edition Method 2540C 17 2 Methods of Chemical Analysis of Water and Wastes EPA 600 4 79 020 Method 160 3 Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 07 25 06 Revision 5 0 I31 TSS 1 of 6 Page RESIDUE TOTAL SUSPENDED Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE SM 2540 D Effective Date 081106 1 0 Scope and Application Ts 1 This method is applicable to all aqueous samples 2 0 Working Range 2 1 The working range is 5mg L the reporting limit to 2000mg L 3 0 Method Summary 3 4 0 4 1 A measured volume of sample is filtered through a pretared filter The residue that remains on this filter after drying in a 105 degree Celsius oven is considered the suspended solid portion of the sample Sample Collection Preservation and Holding Time 1 The sample must be unpreserved It must be stored at 4 degrees Celsius until analysis Analysis must take place within 7 days of sampling per CFR part 136 Table 5 0 Interferences 5 5 1 2 Non representative particulates such as leaves rocks and sticks may be excluded To avoid water entrapment limit the sample size to that yielding no more than 200mg residue on the filter This would be a final result of 2000mg L since we a
160. anks Three types of blanks are required for this method A calibration blank is used to establish the analytical calibration curve the laboratory reagent blank is used to assess possible contamination from the sample preparation procedure and to assess spectral background and the rinse blank is used to flush the instrument between samples in order to reduce memory interferences 7 6 1 Calibration blank Consists of 2 v v nitric acid and 1 HCl in reagent grade water with internal standards 7 6 2 Laboratory reagent blank LRB or Method Blank MB Consists of 2 v v nitric acid and 1 HCl in reagent grade water with internal standards The LRB is carried through the entire sample digestion and preparation scheme as the samples including digestion when applicable 7 6 3 Rinse blank Consists of 2 v v nitric acid and 200ug L Au in reagent grade water Tuning Solution Daily Performance Check This solution is used for instrument tuning and mass calibration prior to analysis The solution is Revision 3 0 M12 200 8 Page 9 of 26 7 8 7 9 purchased from Perkin Elmer It contains Ba Cd Ce Cu Pb Mg Rh and U at 10 ng mL 0 5 in 1 HNO3 The quality control sample is the initial calibration verification solution ICV which is prepared in the same acid matrix as the calibration standards This solution is an independent standard near the midpoint of the linear range at a concentration other th
161. anyon Lake Nutrient TMDL QAPP Page 17 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE The SJRIPP monitoring program includes the following tasks Identification of Dumping Sites County Code Enforcement staff will assess recent illegal dumping complaints and do field reconnaissance to identify any new sites within the project area Identified historical and current dumping sites will be categorized to the extent feasible based on records and visual observations into the following categories included in Table 5 Table 5 SJRIPP Waste Characterization Table Constituent Unit of Measure Woody Debris Cubic Feet Inert Construction Waste Cubic Feet Automotive Batteries Oil Paint and other Hazardous Household Wastes ABOP HHW Gallons Cubic Feet Residential Illegal Dumping Cubic Feet Hazardous Industrial Waste Gallons Cubic Feet Other As Appropriate Illegal dump sites containing hazardous wastes will be further characterized by the County Department of Environmental Health as necessary to ensure safe and proper clean up and disposal of such wastes Water quality samples collected under this program will be monitored for the 14 water quality constituents listed in Table 6 Table 6 SJRIPP Constituents to be Monitored total Kjeldahl nitrogen TKN total copper total nitrogen TN total lead Pbiotai E coli total zinc ZNiotai turbidity
162. are spiked at the reporting limit or 2 5 10 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit 7 8 1 Onan annual basis perform the LOD verification check Spike QC sample of reagent water at a level of no more than 2 3 times analyte MDL Analyte response must be greater than method blank response Demonstration of Capability Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 7 10 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 8 0 Procedure 8 1 Sample Preparation 8 1 1 Distillation is required for all samples under the NPDES permit program First check the distillation comparison study records If a sample from the same site has been distilled in the past and the RPD between the distilled and un
163. as been properly preserved If properly acid preserved the sample can be held up to 6 months before analysis for all metals except mercury which can be held for 28 days For the determination of dissolved elements the sample is filtered through a 0 45 um pore diameter membrane filter at the time of collection or as soon thereafter as practically possible Use a portion of the sample to rinse the acid rinsed filter flask discard this portion and collect the required volume of filtrate Acidify the filtrate with 1 1 nitric acid immediately following filtration to pH 2 Filter a blank and attach QBfil For the determination of total recoverable elements in aqueous samples samples are not filtered but acidified with 1 1 nitric acid to pH lt 2 Preservation may be done at the time of collection however to avoid the hazards of strong acids in the field transport restrictions and possible contamination most samples are returned to the laboratory within two weeks of collection and Revision 3 0 MI2 200 8 Page 10 8 4 8 5 of 26 acid preserved upon receipt in the laboratory Following acidification the sample is mixed and the pH is verified If for some reason such as high alkalinity the sample pH is verified to be gt 2 more acid is added until verified to pH 2 If after the addition of up to 2 mL of acid per 100 mL of sample the pH is still 22 this is noted in the prep log and N pH is added in LIMS When feasi
164. asis for recommendations that the Regional Board consider revisions to the Implementation Plan Chapter 5 of the Basin Plan to incorporate the nutrient TMDLs for Canyon Lake and Lake Elsinore These recommendations outlined in Resolution No RB8 2004 0037 were adopted by the Regional Board in December 2004 and subsequently approved by the U S EPA on September 30 2005 This plan addresses the requirements of stakeholders to implement a nutrient monitoring program providing the data necessary to review and update the Lake Elsinore and Canyon Lake Nutrient TMDLs as described in the February 15 2006 Lake Elsinore and Canyon Lake Nutrient TMDL Monitoring Plan 2006 Monitoring Plan Although the TASK FORCE will have managerial oversight of all TASK FORCE Monitoring programs the specific lake and watershed monitoring programs are being implemented and paid for by different entities Total maximum daily load TMDL is a calculation of the maximum amount of a pollutant that a waterbody can receive and still meet water quality standards and an allocation of that amount to the pollutant s sources Stakeholders include all signatory members TASK FORCE Members of the Lake Elsinore and Canyon Lake TMDL TASK FORCE Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 12 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE San Jacinto River Improvement and Protection Program In 2004 the County of Riverside was awarded a Phase III
165. aste generated from the Kjeldahl analysis containing mercury is poured into a KjN Only drum which is hauled away by an independent waste hauler 4 4 Chlorinated solvents are recycled whenever possible When this is not feasible the waste is sparged continuously until the contents of the drum has Revision 2 0 S07 Page 2 of 2 an acceptable level of residual solvents The contents are then neutralized and sewered See SOP S06 References The Waste Management Manual for Laboratory Personnel available from the American Chemical Society Less Is Better Laboratory Chemical Management for Waste Reduction available from the American Chemical Society s Department of Government Relations and Science Policy 1155 16th Street N W Washington D C 20036 202 872 4477 Approved by Susann K Thomas Date__ 08 28 06 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX B UNIVERSITY OF CALIFORNIA RIVERSIDE DR MICHAEL ANDERSON LABORATORY STANDARD OPERATION PROCEDURES Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE STANDARD OPERATING PROCEDURES FOR WATER QUALITY MEASUREMENTS Anderson Laboratory Department of Environmental Sciences University of California Riverside Updated 10 30 06 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 3 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE
166. at 20 D O of seeded blank immediately after preparation D O of seeded blank after a 5 day incubation at 20 C P Decimal volumetric fraction of sample used or W 96 of sample in bottle F Ratio of seed in diluted sample to seed in seed control seed in diluted sample seed in seed control Note Since several blanks are prepared during a BOD run the average blank depletion is subtracted from each sample depletion An exception is made if one blank bottle depletes by more than 0 5 from the others The analyst must then evaluate the blank result based on the depletion of the associated LCS If the blank appears to be an anomaly then it is not used in the average If the blank indicates contamination in the dilution water that blank depletion is subtracted from all associated samples and QC Note For in house calculations f is considered to be equivalent to 1 Any variation in f due to sample dilutions is negligible after result is rounded to two significant figures 14 Reporting 14 1 The following criteria 15 followed when choosing a reportable result 14 1 1 Residual DO of at least 1mg L 14 1 2 DO depletion of at least 2mg L Revision 5 0 105 BOD Page 7 of 8 14 2 If more than one dilution meets this criteria the optimal result is chosen 14 2 1 Choose the answer with the least dilution i e the answer which used more of the original sample 14 2 2 If more than one vali
167. ated 2 2 Check the Peer Review Checklist for the following 2 2 1 Raw data matches notations made on the checklist 2 2 2 failures are marked appropriately 2 2 3 The Peer Review Checklist is filled out completely 2 2 4 Initials and signatures are dated 2 2 5 the necessary support data is present 2 2 6 Follow up actions are being taken If it says that RE was created double check in Element that it was done 2 3 Check the data in Element for the following 2 3 1 Raw data matches Element entries 2 3 2 samples and analytes have answers 2 3 3 The bench sheet matches the data in Element 2 3 4 Units and reporting limits are correct 2 3 5 All red data is qualified correctly Check that the qualifiers are correct for the problem associated with the data Remember that there may be some issues that require qualifiers but do not turn red 2 4 You must return the batch to the reporting chemist and ask for additional data if data is missing Do not sign or submit incomplete data packages If you are sending the data back to the analyst change the status to pending 2 5 Once the data is verified set the data status to Analyzed sign and date the Peer Review Checklist as the Peer Reviewer Organic data is submited to the supervisor Inorganic data is returned to the analyst 3 0 Supervisory Review Inorganics and Microbiology 3 1 Query reviewable reports under the following departments in Project Management Qu
168. ation performance data Working range of analytes Reporting limit to 9096 of Linear Dynamic Range Maximum 2 0 SUMMARY OF METHOD 2 1 2 2 An aliquot of a well mixed homogeneous aqueous sample is accurately weighed or measured for sample processing See SOP M02 for information on digestion methods For the determination of dissolved analytes in a filtered aqueous sample aliquot or for the direct analysis total recoverable determination of analytes in drinking water where sample turbidity is 1 NTU the sample is made ready for analysis by the appropriate addition of nitric acid and hydrochloric acid The analysis described in this method involves multielemental determinations by ICP AES The instrument measures characteristic atomic line emission Revision 4 1 M07 200 7 Page 3 of 21 23 spectra by optical spectrometry Samples are nebulized and the resulting aerosol is transported to the plasma torch Element specific emission spectra are produced by a radio frequency inductively coupled plasma The spectra are dispersed by a grating spectrometer and the intensities of the line spectra are monitored at specific wavelengths by a photosensitive device Photocurrents from the photosensitive device are processed and controlled by a computer system background correction technique compensates for variable background contribution to the determination of the analytes Background is measured adjacent to the analyte wavelength duri
169. atory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year Constant Weight Study On an annual basis a constant weight study is performed 200mg of cellulose is placed on three TSS filters by filtering a 100ml aliquot of a 2000mg L solution This solution is intended to represent the most challenging sample Filters are placed in the oven for an hour cooled and weighed This process is Revision 5 0 I31 TSS Page 6 of 6 repeated until the weights are constant Constant weight is defined as weight change less than 0 5mg or 4 of the previous weight whichever is less The constant weight determined by this study will be used as the drying time for the procedure Empty filters are also tested to determine the necessary filter preparation time 10 0 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 11 0 Pollution Prevention and Waste Management SOP S07 Pollution Prevention 12 0 Definitions See SOP Q15 SOP Definitions 13 0 Safety 13 1 General laboratory safety procedures are sufficient for this analysis Recommended safety equipment includes gloves and safety glasses 14 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in
170. ave specific RLs Check with Project Managers 4 6 4 zz analyses are inactive and should not be altered An additional MDL study may be performed for common laboratory contaminants This study consists of the analysis of standards over a period of several days injected into several instruments if applicable LOD Verification The MDL may also be defined as the Limit of Detection or LOD On a yearly basis the validity of the LOD shall be confirmed by qualitative identification of the analyte s in a QC sample in each quality system matrix containing the analyte at no more than 2 3X the LOD for single analyte tests and 1 4X the LOD for multiple analyte tests Analyte response must be greater than method blank response to verify the Level of Detection or MDL for each column or instrument An LOD study is not required for any component for which spiking solutions or quality control samples are not available or when test results are not to be reported to the LOD Revision 7 0 Page 12 of 14 001 5 0 Reporting Limits 5 Reporting limits are established based on MDL studies regulation or client requirements 5 2 The RL may also be defined as the Limit of Quantitation LOQ A yearly LOQ verification study must be performed if the LOD has not been verified as described in section 4 8 52 1 The validity of the LOQ is confirmed by successful analysis of a QC sample containing the analytes of concern in each quality system matrix 1 2 t
171. barrel 13 1 3 Unused distillate or filtrate is placed in the Low Acid Concentration Waste barrel 13 2 See also SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP S07 Pollution Prevention 14 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office Revision 5 0 153 NH3 Page 10 of 10 15 0 References Standard Methods for the Examination of Water and Wastewater APHA AWWA WPCF 18 Edition 4500 NH H SEAL Analytical AQ2 Method No EPA 103 A Rev 4 6 01 05 EPA Method 350 1 Methods for the Chemical Analysis of Waters and Wastes Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 09 18 06 Revision 4 1 M07 200 7 Page 1 of 21 METHOD 200 7 Determination Of Metals And Trace Elements In Water And Wastes By Inductively Coupled Plasma Atomic Emission Spectrometry Standard Operating Procedure of Edward S Babcock amp Sons Effective Date 09 22 06 1 0 SCOPE AND APPLICATION Inductively coupled plasma atomic emission spectrometry ICP AES is used to determine metals and some nonmetals in solution This method is a consolidation of existing methods for water and wastewater Our laboratory does not use this method for the determination of solid samples This method is applicable to the following
172. batch Internal standard methods normally have protocol for evaluating the internal standard recovery in QC and Sample data Two variations on this evaluation process are most common Compare the mean value of the internal standard from the calibration standard and or compare the daily calibration verification internal standard to the internal standards in the QC and Sample data Internal standard response is calculated by chromatography software Internal standard performance is monitored and evaluated based on method specified criteria If internal standards do not satisfy requirements see SOP Q06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager 2 0 External Quality Control 2 Semiannual Check Samples 2 1 1 2 1 2 2 1 3 Every six months certified samples are purchased from an outside source such as Environmental Resource Associates The results of these tests are used to check the accuracy of the analyses within the lab The Quality Control Manager or Supervisor has a copy of the certified results Upon completion of analysis each analyst verifies their result with the QA Department 2 2 Proficiency Testing Samples PT 2 2 2 22 2 253 Check samples are purchased on a periodic basis from a NIST certified vendor to check for the accuracy of analyses in the laboratory The results from these samples are reported to the g
173. be lt 2000 mg L Sect 4 2 Samples may be analyzed directly by pneumatic nebulization without acid digestion if the sample has been properly preserved with acid and has turbidity of lt 1 NTU at the time of analysis This total recoverable determination procedure is referred to as direct analysis This method is not sensitive enough to determine some drinking water analytes without preconcentration The preferred method for those analytes is ICP MS SOP M12 For the determination of total recoverable analytes in aqueous samples a digestion is required prior to analysis when the elements are not in solution e g aqueous samples that may contain particulate and suspended solids See SOP M02 for digestion procedures When determining boron and silica in aqueous samples only plastic PTFE or quartz labware should be used from time of sample collection to completion of analysis Borosilicate glass is avoided to prevent contamination of these analytes Detection limits and linear ranges for the elements will vary with the wavelength selected the spectrometer and the matrices Table 2 provides estimated instrument detection limits for the listed wavelengths However actual method detection limits and linear working ranges will be dependent on the sample matrix instrumentation and selected operating conditions Data quality objectives are understood by the analyst prior to analysis ESB has on file documentation of required initial demonstr
174. be held at SAWPA Copies of versions other than the most current will be discarded so as not to create confusion Each Project Administrator will provide interim and final reports to the Regional Board State Board or other applicable parties consistent with the requirements of their program These reports will describe activities undertaken milestones and any problems encountered in administering the program and shall be submitted per the schedule described in Table 7 Table 7 Project Reporting Requirements Project Reporting Frequency Start Date TMDL TASK FORCE Annually August 15 2006 SJR Component Quarterly June 1 2006 SJRIPP Quarterly October 10 2006 Not later than August 15 2006 and annually thereafter during the life of this agreement the TASK FORCE will provide to the Regional Board all water quality data and QA QC information associated with the data collection All results data will be transmitted in electronic format all associated data will be provided in hard copy Persons responsible for maintaining records for this project are as follows The SJW Quality Assurance Manager will maintain all SJW Nutrient Monitoring Program sample collection records sample transport records chain of custody and field analyses forms and all records submitted by contract laboratories associated with the SJW nutrient monitoring program The LE Quality Assurance Manager will maintain all LE Nutrient Monitoring
175. ble samples are held after preservation for 16 hours prior to withdrawing an aliquot for processing or direct analysis f samples are processed prior 1016 hours a notation is made in the prep log and a qualifier N M is added in LIMS For aqueous samples a field blank should be prepared and analyzed if required by the data user Use the same container and acid as used in sample collection Samples containing turbidity lt 1 NTU will be determined by direct analysis Screen acidified samples by testing an aliquot in a turbidimeter meter Results are recorded in the logbook Samples containing turbidity 1 NTU must be digested prior to analysis 9 QUALITY CONTROL Note See also ESB SOP QO1 for general QC requirements 9 1 9 2 Our laboratory operates a formal quality control QC program The minimum requirements of this program consist of an initial demonstration of laboratory capability and the periodic analysis of laboratory reagent blanks fortified blanks and calibration solutions as a continuing check on performance The laboratory maintains performance records that define the quality of the data thus generated Initial demonstration of Laboratory Performance mandatory 9 2 1 The initial demonstration of performance is used to characterize instrument performance determination of linear calibration ranges and analysis of quality control samples and laboratory performance determination of method detection limits p
176. ble write NA in the space Be sure the batch number date and your initials are on the checklist Include all necessary raw data to support the answers on the checklist Checklist answers must be true and correct 1 3 2 Please complete the comment section with every batch as necessary Please include the following at a minimum if applicable use and justification of secondary column data deviations from the method and the circumstances involved MB LCS Initial Calibration CCV or ICV failures and the reasons for the QC failure if known 1 3 3 If QC failures render a batch unacceptable the analyst must get Supervisor approval to turn in that batch This approval must be documented on the peer review sheet 1 4 Once the data is verified as acceptable change the status to Needs Peer Review and turn data into the peer reviewer Revision 4 0 Q10 Page 2 of 6 2 0 Peer Review Analyst results are verified by a designated peer analyst prior to release of data to the supervisor Any major problems are brought to the supervisor s attention immediately All data packages should be able to stand on their own The peer reviewer performs the following functions 2 1 Check raw data for the following 2 1 1 Calculations are correct Spot check 2 1 2 The batch meets acceptance criteria 2 1 3 Proper documentation concerning QC failures method deviations elimination of calibration points etc 2 1 4 comments or initials are properly d
177. c system maintenance When system performance does not meet the established QC requirements corrective action is required and may include one or more of the following 7 6 1 GC injector ports can be of critical concern especially in the analysis of DDT and Endrin Injectors that are contaminated chemically active or too hot can cause the degradation breakdown of the analytes Endrin and DDT breakdown to endrin aldehyde endrin ketone DDD or DDE When such breakdown is observed clean and deactivate the injector port break off at least 30 cm of the column and remount it Check the injector temperature and lower it to 205 C if required Endrin and DDT breakdown are less of a problem when ambient on column injectors are used 7 6 2 Metal injector body Turn off the oven and remove the analytical columns when the oven has cooled Remove the glass injection port insert instruments with on column injection Lower the injection port temperature to room temperature Inspect the injection port and remove any noticeable foreign material 7 6 2 1 Place a beaker beneath the injector port inside the oven Using a wash bottle serially rinse the entire inside of the injector port with acetone and then toluene catching the rinsate in the beaker 7 6 2 2 Prepare a solution of a deactivating agent Sylon CT or equivalent following manufacturer s directions After all metal surfaces inside the injector body have been thoroughly coated with the deac
178. cal Monitoring The SJRIPP will attempt to collect water quality data from within Kabian Park during both dry and wet weather conditions If illegal dump sites are identified within flowing receiving waters during dry weather water quality samples of appropriate constituents based on the identified waste will be collected upstream and downstream of a representative site before the site is cleaned After the site is cleaned a follow up water quality sample for the same constituents will also be collected If dump sites within Kabian Park are identified in watersheds tributary to ephemeral receiving waters that will likely receive sufficient flow to sample during wet weather the SJRIPP staff will attempt to collect wet weather samples upstream and downstream of the dumping areas in the receiving water of the watershed believed to be most impacted by illegal dumping presuming sufficient flow Any chemical monitoring will be conducted in conformance with the procedures specified within this QAPP Specific constituents monitored will depend on the identified sources within the illegal dump site Parameters to be collected through the program are presented in Table 6 At the end of the SJRIPP Riverside County will provide a full listing and summary of the data collected as part of the SJRIPP interim and final grant progress reports The final grant progress report is due by January 2008 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 19 Lake
179. centration Only orthophosphate forms a blue color in this test 4 0 Sample Preservation 4 1 Samples must be unpreserved and stored in the refrigerator 4 2 Analysis must be done within 48 hours 5 0 Interferences 5 1 Copper iron or silicate at concentrations many times greater than their reported concentration in Seawater causes no interference However high iron concentrations can cause precipitation of and subsequent loss of phosphorus 5 2Arsenate is determined similarly to phosphorus reacting with molybdate reagent to produce a blue color and should be considered when present in concentrations higher than phosphorus Concentrations as low as O0 1mg As L can interfere 5 3Hexavalent chromium and nitrite interfere to give results about 3 lower at concentrations of 1mg L and 10 15 lower at 10mg L 6 0 Safety Revision 5 0 OP Page 3 of 9 I27 General laboratory safety procedures are sufficient for this analysis Recommended safety equipment includes gloves and safety glasses 7 0 Equipment Standard laboratory glassware volumetric flasks beakers graduated cylinders pipettes 7 2 Syringe and 0 45 micron filter disk Test each new lot of filters by comparing an unfiltered and filtered LCS and a Blank Zero the spectrophotometer with an unfil document the result for the fil Tea Spectrophotometer Spectronic Spectronic
180. ceptance is 1 2 the RL and this value is MDL method blanks will be considered ND below the MDL 2 8 Sample results that require a J flag will be reviewed by the Project Manager to determine where qualifiers are necessary i e If results are less than ten times the level detected in the method blank the proper qualifier NBLK is placed on the sample 2 9 Travel Blanks See ESB SOP 01 section 1 2 6 Revision 7 0 006 Page 4 of 11 3 0 Spikes and Duplicates 3 1 3 2 3 9 34 3 9 3 6 3 7 When a spike or duplicate is out of the laboratory acceptance criteria that sample result is called into question not batch acceptance If the sample background is 4 times or greater than the fortification concentration the spike is considered invalid and follow up is not necessary Attach the proper qualifier to the spike QM 4X Duplicates must meet the RPD criteria unless the sample concentration is lt 10 times the reporting limit If the sample concentration is lt 10 times the reporting limit the analysis should be reviewed whenever the difference between the sample and the duplicate is greater than the reporting limit Attach the proper qualifier to the duplicate QRPDI The above may not be appropriate for some analyses See specific method SOP for details When an MS MSD or DUP fails to meet the laboratory prescribed acceptance criteria for either percent recovery or RPD a follow up must be performe
181. ces in measured values for turbidity even though the same suspension is used for fol calibration To minimize such differences the owing design criteria are observed Des 5 5 5 St beakers graduated cylinders pipets Note All glassware is cleaned immediately prior to and after use by 4 1 Light source Tungsten lamp operated at a color temperature between 2200 3000 K 4 2 Distance traversed by incident light and Scattered light within the sample tube Total not to exceed 10 cm 4 3 Detector Centered at 90 to the incident light path and not to exceed 30 C from 90 C The Detector and filter system if used shall have a spectral peak response between 400 and 600 nm andard laboratory glassware volumetric flasks thorough rinsing with three portions of NANOPURE water f glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final NANOPURE rinse 6 0 Reagents and Standards 6 1Turbidity free water Nanopure water is used It has 0 05 a background turbidity reading of approximately NIU 6 2Stock formazin turbidity suspension 4000 NTU Form azine Solution purchased for supplier stored at room temperature until Manufacturer specified expi soon prob from ration date S
182. ch bottle D O that is to be placed in the incubator with plastic cup caps Put the covered bottles in the incubator 11 2 9 After incubating D O samples for 5 days determine the final Dissolved Oxygen see Dissolved Oxygen procedure on the D O bottles 113 Other Products 11 3 1 BOD dissolved dissolved BOD Filter sample though 0 45 micron filter prior to analysis Do the same to a blank and duplicate sample Filter 120 mL of Nanopure water and set up a 40 dilution for the method blank 11 3 2 BOD Carb cabonaceous BOD Add 0 16g Nitrification Inhibitor containing 2 chloro 6 trichloro methyl pyridine TCMP to BOD bottle containing sample Do the same to a blank LCS and duplicate sample 11 4 Other matrices such as solids and sludges Discuss with a supervisor Perform a duplicate on a solid or sludge sample 12 Quality Control Revision 5 0 IOS BOD Page 5 of 8 Note See also ESB SOP QO for general QC requirements 12 1 Blanks are analyzed with every 20 samples or one per batch whichever is more to check for possible interference from seed and reagents Blanks are reported per matrix type The target range is lt 0 5 mg L DO An average blank value from the batch is subtracted out of the sample results Analysts should double check DO readings and notify a supervisor if blank readings exceed the target range 12 2 Duplicate analyses are performed at a frequency of in 20 sampl
183. conox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 6 9 Stock Standards 6 9 1 Cellulose stored at room temperature for up to 10 years 6 10 Lab Control 500mg of cellulose is weighed into a liter of D I water This solution is kept at room temperature for up to a 6 months Use a 100mL aliquot 6 11 Reagent water D I water Revision 5 0 I31 TSS Page 3 of 6 7 0 Procedure 7 1 Prepare glass fiber filters by rinsing three times with D I water and heating at 105 C for a minimum of 1 hour constant weight study is performed yearly to establish the minimum time required to bring the filter to a constant weight 7 2 Take hot filters out of 105 C oven 7 3 Cool filters to room temperature then place in a desiccator Use forceps when handling filters Place filter on balance and record tare weight Place the filter onto the filtering apparatus Wet filter with a small amount of D I to seat it 7 4 Mix sample well by shaking sample bottle Measur an appropriate volume of sample in a graduated cylinder normally 100 mL Use a 200 mL sample volume for method blank and samples expected to contain very minute amounts of suspended material Filter through apparatus collecting suspended residue on filter Rinse cylinder and filter 2 to 3 times with a small amount of D I water Apply suction th
184. containers Staff Gauge Depth Meter Depth Lab No Water Temp pH Cond Observations SAMPLE Time 24 hr clock Date Number of containers Staff Gauge Depth Meter Depth Lab No Water Temp pH Cond Observations Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 46 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE San Jacinto River Watershed TMDL Field Data Sheet Field Observation Suggestions Odor Color Clarity Floatable Settable Weeds Biology Structural Sky Wind Flow None Musty Sewage Rotten egg Sour milk Fishy Other None Yellow Brown Grey Green Red Other Clear Cloudy Opaque Suspended solids Other None Oil sheen Foam Animal waste Green waste Food Paper Plastic Grease Hydrophytes Trash Other None Salt Clay Oil Rust Microbes Other None Normal Excessive Note Unobserved Algae bloom Larvae Crawfish Frogs Fish Water fowl Hydrophytes Blue green algae Other Normal Cracking Spauling Note Stormy Overcast Partial clouds Haze Fog Clear Calm Light breeze Strong breeze Windy Gusts Storm Flood Rapid Tranquil Laminar Standing Dry Note Any condition that seems noteworthy place on this line Also use the back of the field sheet for additional information Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 47 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE ATTACHMENT 2 EXAMPLE UCR IN LAKE
185. covery of the four replicates must be 80 120 with a maximum RSD of 10 9 5 Demonstration of Continuing Proficiency an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 9 6An MDL study is completed whenever major equipment or procedural changes are made Standards are Spiked at a concentration 2 5 5 times the estimated MDL and a minimum of seven replicates analyzed See QA manual for calculation Results must be below the reporting limit Revision 5 0 I36 Turbidity Page 7 of 7 9 6 1LOD Verification an annual basis an aliquot of water is spiked at a level of 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL 10 0 Definitions SOP 015 SOP Definitions 11 0 Safety General laboratory safety procedures are adequate for this analysis 12 0 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 13 0 Pollution Prevention and Waste Management See SOP S07 Pollution Prevention 14 0 Metho
186. ct injected uL The injection volume for samples and calibration standards is the same For purge and trap analysis Vi is not applicable and therefore is set at 1 Vs Volume of the aqueous sample extracted in mL If units of liters are used for this term multiply the results by 1000 Using the units specified here for these terms will result in a concentration in units of ng mL which is equivalent to ug L 7 4 8 2 For non aqueous samples Ax V D Concentration ug kg CF Vi Ws where Ax Vt D CF and Vi are the same as for aqueous samples and Ws Weight of sample extracted g The wet weight or dry weight may be used depending upon the specific application of the data If units of kilograms are used for this term multiply the results by 1000 Using the units specified here for these terms will result in a concentration in units of ng g which is equivalent to ug kg Revision 4 0 Page 12 of 16 7 4 9 7 4 10 7 4 11 7 4 12 7 4 13 7 4 14 7 4 15 O54 8081 7 4 8 3 If the responses exceed the calibration range of the system dilute the extract and reanalyze Peak height measurements are recommended over peak area integration when overlapping peaks cause errors in area integration Each sample analysis must be bracketed with an acceptable initial calibration calibration verification standard s or calibration standards interspersed within the samples The results from these brack
187. culant has settled to approximately half the bottle volume mix and allow it to settle once more 10 1 6 Add 1 ml of Sulfuric Acid 10 1 7 Mix by inverting several times until flocculant is completely dissolved Revision 4 0 124 DO Page 4 of 6 10 1 8 Measure a volume corresponding to 201 ml original sample after correction for sample loss by displacement with reagents and pour into beaker 10 1 9 Add a few drops of starch solution to form a blue color Drain the tip of the titration buret and titrate with 0 025 M NazS 703 solution until the disappearance of the blue color Disregard subsequent recolorations 10 2 D O Probe Calibration 10 2 1 Air Calibration Check 10 2 1 1 Dry membrane and place in BOD bottle containing 50mL Nanopure 10 2 1 2 Press calibration mode 10 2 1 3 Wait approximately 15 minutes for probe to stabilize 10 2 1 4 If necessary adjust saturation percentage to 96 Note For probe calibration operation and maintenance see YSI Model 5000 Operations Manual section 6 1 page 21 and section 7 1 page 26 See also YSI 5905 5010 BOD Probe Instruction Manual for further details If the membrane is replaced refill the solution and allow probe to sit for a half hour 10 2 2 Winkler Calibration Check 10 2 2 1 Blank 10 2 2 1 1 Set up a BOD bottle filled with bubbled unseeded water 10 2 2 1 2 Probe Blank Set meter in Main mode and take a DO reading 10 2 2 1 3 Winkler Blan
188. curves More than a three point calibration is recommended for nonlinear curves For 8000 series methods a five point calibration is required for a linear first order model six point calibration for a quadratic second order model and seven point for a polynomial third order model The analyst has the option to use linear or nonlinear integration and to force include or ignore the origin depending on method requirements The analyst may decide to exclude a calibration point if it appears to be invalid under the following conditions The curve will still contain the minimum number of points required without the excluded point A standard at or below the reporting limit is included No sample result is reported above the high calibrator unless qualified The analyst documents reasoning for eliminating a calibrator Note If a point is eliminated it is recommended that the analyst verify that portion of the curve with a QC sample Revision 7 0 QOI Page 9 of 14 3 2 3 3 Note The analyst may replace the above calibrator with a standard injected later in the run e g extra CCV as long as the new calibration can be validated with method prescribed ICVs and CCVs Calibration Levels 32 Thelowest calibration standard is above the analyte MDL 3 2 2 low standard must be at or below the reporting limit 3 2 3 Other calibration standards include those that are at or below the regulatory limit if known
189. cutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies performed twice a year 11 0 Safety 11 1 See SOP 501 Concentrated Acids and Bases SOP S02 Compressed Gas Cylinder Handling SOP S03 Spill Control Policy 11 2 General laboratory safety procedures are sufficient for this analysis Recommended safety equipment includes gloves and safety glasses Revision 5 0 26 Page 9 of 9 12 0 Corrective Action For Out of Control Or Unacceptable Data 12 1 See SOP Q06 Corrective Action 13 0 Pollution Prevention and Waste Management 13 1 Waste Disposal 13 1 1 Instrument waste is placed in the Low Acid Concentration Waste barrel 13 1 2 Sample waste is placed in the Low Acid Concentration Waste barrel 13 2 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP 507 Pollution Prevention 14 0 Method Performance 14 1 See Method 415 1 section 9 SM 5310B section 6 14 2 Our intralaboratory generated data is expected to achieve similar results Refer to MDL studies Initial Demonstration of Capability Studies and quality control charts maintained in the QC Office References EPA 415 1 1974 Methods for the Chemical Analysis of Waters and
190. d unless 3 4 1 Sections 3 2 or 3 3 apply 3 4 2 The sample is obviously non homogeneous and any attempts to reproduce the same sample aliquot is unlikely attach QRPDo and QFnoH to QC and NRPDh to samples 3 4 3 MS recovery and RPD are acceptable attach qualifier QMSD unless the analyst is using the MSD to satisfy MS frequency requirements specified by the method 3 4 4 Sample matrix problems are obvious i e interfering peaks a physical attribute of the sample that hinders normal analysis Attach QMint to the QC and NMint to the sample 3 4 5 There is reasonable evidence documented with the raw data to suspect that the spiking solution was made incorrectly If possible evaluate recovery based on the new spiking level A qualifier is not necessary If this is not possible attach qualifiers QMout and QFspk For MS MSD results over calibration range 3 5 1 Ifthe result is acceptable report with QOcal qualifier 3 5 2 Ifthe result is unacceptable Dilute and rerun Any analyte falling outside the acceptance criteria must be flagged QMout or QRPDo The sample used for the spike or duplicate must be flagged NMout NMoRo or NRPDo Ideally the spike or duplicate should be reanalyzed during the initial analytical run and the final post follow up data entered into the computer If Revision 7 0 006 Page 5 of 11 3 8 3 9 the retry is still out of acceptance criteria in the original batch attach QFob to the QC and N
191. d Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office References 1 EPA Method 180 1 1993 Methods for the Chemical Analysis of Waters and Wastes 2 Standard Methods for the Examination of Water Wastewater APHA AWWA WEF 18th Edition Method 2130B Note All italicized items are an indication of a variation from the method Approved by Susan K Thomas Date 10 02 06 Revision 5 0 T42 TP Page 1 of10 TOTAL PHOSPHORUS Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE ASCORBIC ACID METHOD SM 4500 P B 4 E Date Effective 082806 1 0 Scope and Application These methods cover the determination of specified forms of phosphorus in drinking surface and saline waters domestic and industrial wastes 1 1 Health Effects of Phosphorus 1 1 1 Too much phosphate can cause health problems such as kidney damage and osteoporosis While burning white phosphorus may cause damage to the liver the heart or the kidneys 1 2 Environmental Effects of Phosphorus 1 2 1In water white phosphorus will accumulate in the bodies of aquatic organisms In soil phosphorus will remain for several days but in deep soils and the bottom of rivers and lakes phosphorus will remain for a thousand years or so Orthophosphates applied to agricultural or reside
192. d answer is available and they differ greatly refer to historical data COD or TDS result to pick the result that will fit best 14 3 If the above criteria are not met the supervisor is consulted to determine the most appropriate course of action 14 3 1 Ifresidual DO is 1 mg L then too much sample was used Qualify the sample as follows 14 3 1 1 A greater than result will be reported using the _BOD qualifier The greater than value is calculated as the highest value that the sample could have been had its smallest dilution depleted to 1 0mg L Use also qualifier N Nae result not available due to lab error 14 3 2 If DO depletion 2mg L then insufficient sample was used Qualify the sample as follows 14 3 2 1 Data will be reported using BOD qualifier with an adjusted reporting limit based on sample size This qualifier allows the result to be displayed even though it is less than the elevated reporting limit Add N BOD to explain results did not meet method calculation criteria The reported result is an estimated value only 14 3 2 2 Exceptions to this rule include samples with a dilution of 596 or greater in those cases no qualifications are necessary and the client will see ND at an RL of 40mg L or less 14 3 3 Each of the above scenarios requires that a BOD cancellation form be filled out with estimated results and client information 14 3 3 1 Write Do not recalc in the top left hand corner Go into Update
193. d at a frequency of no less than one per 10 samples Duplicate analyses of field splits will be used to assess the precision of analytical methods Duplicate analysis of a sample on the same instrument will provide instrumental precision data The relative percent difference RPD of duplicates will be calculated as follows RPD 2 100 where C and are concentrations of analyte in replicate samples 1 and 2 A control limit of 15 will be used for relative percent difference for most analyses Table 2 Accuracy of analytical data will be evaluated by analyzing reference materials and spiked samples where available laboratory measurements only Reference materials will be run with each batch of samples during laboratory analyses Confidence intervals supplied with reference samples will be used as control limits at the 95 confidence level The relative percent error RPE of standards will be calculated as follows RPE 100 where C is the concentration analyzed the sample and C is the true concentration Spiked samples will be used to assess the recovery of various analytes in laboratory measurements only Spikes will contain analytes at the level present in the sample or at the concentration of the mid range calibration standard whichever is higher Spike recovery will be calculated as follows Recovery A A S 100 where A is the amount of analyte in the spiked sample A is t
194. d at the end of sample analysis In the event that a failure in the sampling or field measurement system occurs the project manager Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 37 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE will be responsible for corrective action The project manager will determine the corrective actions which may include rescheduling the sampling event obtaining different sampling equipment from other entities or taking discrete samples and completing analysis in the laboratory San Jacinto Watershed and SJRIPP Monitoring Programs An Oakton Waterproof pHTestr 2 is used to make field pH measurements It is calibrated prior to each sampling event by dipping the electrode in a buffer solution of either pH 4 7 or 10 Instructions for the Oakton Waterproof pHTestr 2 are included as Appendix F An Oakton TDSTestr 20 is used to make field TDS measurements It is calibrated prior to each sampling event by dipping the electrode into either a 2764 uS or 1413 uS standard solution provided by Oakton Instructions for the Oakton TDSTestr 20 are included as Appendix G A Cooper digital thermometer is used to make field temperature measurements It does not have a calibration feature Lake Elsinore and Canyon Lake Monitoring Programs A Hydrolab DataSonde4a multiparameter water quality monitoring probe or equivalent will be used to make field measurements The immersible probe is fitted with a pressure
195. d calibration routine to be used for sample analysis These documented data must be kept on file and be available for review by the data user 10 3 After completing the initial demonstration of performance but before analyzing samples the laboratory must establish and initially verify an interelement spectral interference correction routine to be used during sample analysis A general description concerning spectral interference and the analytical requirements for background correction and for correction of interelement spectral interference in particular is given in Section 4 1 To determine the appropriate location for background correction and to establish the interelement interference correction routine repeated spectral scan about the analyte wavelength and repeated analyses of the single element solutions Revision 4 1 Page 15 of 21 M07 200 7 may be required Criteria for determining an interelement spectral interference is an apparent positive or negative concentration on the analyte at the MDL level Once established the entire routine must be initially and periodically verified by successful analysis of the SIC blank and check solution with each run or whenever there is a change in instrument operating conditions 11 0 PROCEDURE 11 1 Aqueous Sample Preparation Dissolved Analytes 11 1 1 Samples are received from the splitter filtered through a 0 45 um filter and preserved The sample is then processed like the samp
196. d drinking water It may also be used for determination of total recoverable element concentrations in these waters as well as wastewater This method is applicable to the following elements ANALYTE CAS MCL ppb ANALYTE CAS MCL Aluminum Al 7429 90 5 Mercury Hg 7439 97 6 1000 2 Antimony Sb 7440 36 0 Molybdenum Mo 7439 98 7 6 Arsenic As 7440 38 2 Nickel Ni 7440 02 0 50 100 Barium Ba 7440 39 3 Selenium Se 7782 49 2 1000 50 Beryllium Be 7440 41 7 Silver Ag 7440 22 4 4 100 Cadmium Cd 7440 43 9 Thallium TI 7440 28 0 2 5 Thorium Th 7440 29 1 Chromium Cr 7440 47 3 50 Tin Sn 7440 31 5 Cobalt Co 7440 48 4 Copper Cu 7440 50 8 Uranium U 7440 61 1 1000 Lead Pb 7439 92 1 Vanadium V 7440 62 2 15 Manganese Mn 7439 96 5 50 Zinc Zn 7440 66 6 5000 Analytes in parenthesis are not NELAP certified INSTRUMENTATION ICP MS Reporting limits for these elements are listed in Element attachment Method detection limits MDLs and linear working ranges determined by the lab will be dependent on the sample matrix instrumentation and selected operating conditions Working range waters RL 1000ppb wastewater RL 2900ppb Revision 3 0 M12 200 8 Page 2 of 26 1 2 1 3 1 4 1 5 1 6 1 1 8 1 9 For reference where this method is approved for use in compliance monitoring programs e g Clean Water Act NPDES or Safe Drinking Water Act SDWA
197. d only when resloping is necessary 11 4 8 13 At the end of the run analyze 500 ug L linearity check standard followed by a CCB to verify sufficient rinse time Linearity is dependent of 90 110 recovery 11 4 8 14 Follow instructions in the ELAN 6000 or 9000 Software Manual for printing reports 12 DATA ANALYSIS AND CALCULATIONS 12 1 Elemental equations recommended for sample data calculations are listed in Table 5 Sample data is reported in units of ug L for aqueous samples Do not report element concentrations below the determined MDL 123 Two significant figures are used for reporting element concentrations Revision 3 0 M12 200 8 Page 20 of 26 12 3 For aqueous samples prepared by total recoverable procedure Sect 11 2 the preparation dilution factor is entered into Element as the initial final volume If additional dilutions were made to any samples at the instrument the appropriate factor is applied to calculate sample concentrations by entering a value into the dilution column in Element 12 4 Data values are corrected for instrument drift or sample matrix induced interferences by the application of internal standardization Corrections for characterized spectral interferences are applied to the data Chloride interference corrections are made on all samples regardless of the addition of hydrochloric acid as the chloride ion is a common constituent of environmental samples 125 The QC data obtained during the anal
198. d the entire run the batch must be reanalyzed In some cases however additional sample may not be available for reanalysis In this case either the tests are canceled the client is informed and given the option to resample or results are reported with the proper qualifier NLOhi or NLOlo 1 5 Organic determinations with 11 or more compounds in the LCS 1 5 1 1 5 2 1 5 3 1 5 4 1 5 5 If a large number of analytes are in the LCS it becomes statistically likely that a few will be outside control limits This may not indicate that the system is out of control therefore corrective action may not be necessary Upper and lower marginal exceedance ME limits can be established to determine when corrective action is necessary A ME is defined as being beyond the LCS control limit 3 standard deviations but within the ME limits ME limits are between 3 and 4 standard deviations around the mean ME 4s limit minimum is 10 One marginal exceedance is allowed in an LCS containing 11 16 analytes QLpas If more analytes exceed the LCS control limits or if any one analyte exceeds the ME limits the LCS fails and corrective action is necessary QLout If the LCS fails then one of the following must happen 1 5 4 1 A MS or MSD from a noncalibration source falls within the LCS laboratory acceptance criteria and may replace the LCS QL MS 1 5 42 AnLCSD may be used in place of the LCS unless the LCSD is also required by the method 1 5
199. dard again 11 3 Analysis 11 3 1 Fill vials with sample Shake sample and filter through a 0 2 um disc filter 11 3 2 Start the autosampler on vial 1 through 64 11 3 2 1 Press lt START gt enter 11 3 2 2 Init V 1 enter 11 3 2 3 Rinse 0 enter 11 3 2 4 Last V lt of last vial enter 11 3 3 Make sure the peaknet software 15 calculating appropriately by observing peak heights and retention times 11 4 Shutdown 11 4 1 Under Run load stop method 11 4 2 Turn pressure valve to 0 psi 11 5 Check system calibration daily and if required recalibrate as described in Section 9 11 6 The injection loop is flushed thoroughly using each new sample The same size loop is used for standards and samples Record the resulting peak size in area or peak height units 11 7 The width of the retention time window used to make identifications is based on measurements of actual retention time variations over the course of a day Three times the standard deviation of a retention time is used to calculate the window size unless experience shows that the window requires adjustment The experience of the analyst weighs heavily in the interpretation of chromatograms The current window is 0 5 minutes for chloride and nitrate and 0 75 minutes for sulfate 11 8 Ifa sample analyte concentration exceeds the calibration range the sample is diluted to fall within the range Samples with results near but above the reporting limit are reanalyz
200. dation Check 50ppb 100ppb Dilute 500uL of stock standard 1ppm 2ppm into 10 mL of 90 hexane 10 acetone Revision 4 0 Page 7 of 16 O54 8081 6 0 SAMPLE COLLECTION PRESERVATION AND HANDLING 6 1 Grab samples are collected in glass containers Conventional sampling practices are followed however the bottle must not be prerinsed with sample before collection 6 2 SAMPLE PRESERVATION 6 2 1 6 2 2 6 2 3 Samples are taken from nonchlorinated sources Samples are iced or refrigerated at 4 C from the time of collection until extraction Preservation study results indicate that most of the target analytes present in the samples are stable for 7 days for aqueous samples and 14 days for nonaqueous sample when stored under these conditions 6 3 Extracts are stored under refrigeration in the dark and analyzed within 40 days of extraction 7 0 PROCEDURE 7 1 Sample extraction In general water samples are extracted at a neutral pH with methylene chloride using a separatory funnel Method 3510 SOP O05 Solid samples are extracted with hexane acetone 1 1 sonication extraction Method 3550 SOP O51 7 2 Extract cleanup Cleanup procedures may not be necessary for a relatively clean sample matrix but most extracts from environmental and waste samples will require additional preparation before analysis The specific cleanup procedure used will depend on the nature of the sample to be analyzed and the data quality objectives fo
201. day whichever is more A precision criterion is generated from historical data as described in Standard Methods 9020 VI Results gt 10 times the reporting limit are evaluated against the precision criterion Attach the qualifier N Brp to duplicates that do not meet acceptance criteria If duplicates are extremely erratic report the higher result with the qualifier N Bru and notify the client 12 3 Completed Phase The completed test is run on a quarterly basis 12 3 1 12 3 2 A completed test is used to establish definitely the presence of coliform bacteria and to provide quality control data A positive green bile tube containing is streaked on an eosin methylene blue agar dish The streaking method must ensure presence of some discrete colonies after a 24 2 hour incubation period at 35 C 0 5 The colonies which grow on the E M B agar dish fall in two categories typical and atypical The typical colonies are nucleated with or without a metallic sheen The atypical colonies are unnucleated opaque and mucoid From the plate pick one or more typical well isolated colonies and transfer to a tube of lauryl sulfate broth Incubate this tube at 35 0 5 C for 24 2 hours If no gas production is observed reincubate for an additional 24 3 hours Formation of gas within this lauryl sulfate broth tube within the 48 3 hour incubation period demonstrates the presence of a member of the coliform group Completed test re
202. distilled results is less than or equal to 20 then the sample does not need to be distilled Raw results 1 0 mg L will not generate useful RPD statistics Instead these results must be within 0 1 mg L of each other to eliminate the distillation step in the future If a sample site is not in the study then it must be distilled and added to the study 8 1 1 1 If the apparatus sits idle for an extended period of time or if samples have left a residue clean the apparatus as follows 8 1 1 1 1 Rinse all glassware with D I 8 1 1 1 2 Make clean out solution by adding 25 mL of borate buffer to 500 mL of D I Adjust pH to 9 5 with 6N NaOH solution Fine tune with 1N NaOH Revision 5 0 Page 7 of 10 8 1 2 I53 NH3 8 1 1 1 3 Hill distillation flasks to the line with clean out solution Add boiling chips 8 1 1 1 4 Distill over at least 30 mL 8 1 1 1 5 Re rinse all glassware 8 1 1 2 Then add 50 mL of sample LCS MS MSD and D I method blank to individual distillation flasks 8 1 13 Add 2 5 mL of borate buffer to each flask 8 1 1 4 Adjust to pH 9 5 with IN or 6N NaOH 8 1 1 5 Add several porous VWR boiling chips 8 1 1 6 Distill at 190 C into an Erlenmeyer flask containing 5 mL of 0 04N sulfuric acid Ensure that the tip of the delivery tube is placed below the sulfuric acid level 8 1 1 7 Collect 50ml of distillate 8 1 1 8 Move the delivery tube out of the distillate add extra water to the distillation flask to prevent dryness u
203. droscopic and will require prolonged drying desiccation and rapid weighing 6 2 Samples containing high concentrations of bicarbonate will require careful and possibly prolonged drying at 180 C to insure that all the bicarbonate is converted to carbonate 6 3 Too much residue in the evaporating dish will crust over and entrap water that will not be driven off during drying Total residue in the dish should be limited to about 200 mg 7 0 Safety General laboratory safety procedures apply Care should be taken when reaching over the hot water bath handling dishes or reaching into the ovens 8 0 Apparatus 8 1 500 ml side arm flask 8 2 Filtration apparatus Membrane filter funnel with a Gelman type 47mm 90mm A E glass fiber filter disk 8 3 Drying oven for operation at 180 C 2 C 8 4 Vacuum aspirator 8 5 Desiccator with fresh desiccant 8 6 Balance 78 with a sensitivity of 0 1 mg Calibrated on a daily basis with 5g and 100g class S weights on a daily basis Calibration must be within Revision 5 0 I29 TDS Page 4 of 8 5mg If values are not within these limits recalibrate the balance 8 7 12 Unit steam bath On a quarterly basis drain the water bath and scrap out the residue Try to turn off the bath heat at night so that cool water can circulate 8 8 Standard laboratory glassware volumetric flasks beakers graduated cylinders pipets Note All glassware
204. ds will be checked visually and recorded as checked by initials and dates The Quality Assurance Managers will do all reviews and the TASK FORCE Program Coordinator will perform a check of 10 of the reports The contract laboratory s Quality Assurance Officers will perform checks of all of its records and the contract s Laboratory Director will recheck 10 All checks by the contract laboratory will be reviewed by appropriate TASK FORCE personnel Issues will be noted Reconciliation and correction will be done by a committee composed of the Field Supervisor Analyst and appropriate Quality Assurance Manager and the contract laboratory s Quality Assurance Officer and Laboratory Director Any corrections require a unanimous agreement that the correction is appropriate D3 RECONCILIATION WITH DATA QUALITY OBJECTIVES The project needs a sufficient number of data points as represented by the completeness data quality objective in order to do trend analyses for the Lake Elsinore and Canyon Lake Nutrient TMDLs However natural variability as well as seasonal trends in water quality will be reflected in measured water quality along with variability from lake and watershed management actions such as recycled water addition and aeration system operation in Lake Elsinore Thus careful consideration of natural variability will be necessary Additionally if data are not sufficiently complete the variability in the data may result in a large TMD
205. e 6 of 6 estimated MDL and a minimum of seven consecutive replicates is analyzed See QA Manual for calculation Results must be below the reporting limit LOD Verification On a yearly basis a QC sample is spiked at a level of not more than 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than the method blank response to verify the Level of Detection or MDL Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL Ihe average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 Demonstration of Continuing Proficiency an annual basis each analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 10 0 Reporting 10 1 Results are reported as mg L Nitrite N 10 2 The reporting limit is 0 1 mg L 10 3 The results are reported to 2 significant figures 11 0 Definitions See SOP Q1
206. e amp Canyon Lake Nutrient TMDL TASK FORCE B4 ANALYTICAL METHODS REQUIREMENTS San Jacinto Watershed Nutrient TMDL and SJRIPP Monitoring Program Analytical methods used within the Lake Elsinore and Canyon Lake Nutrient TMDL Monitoring program and SJRIPP Monitoring Program will follow the State of California and the U S EPA approved standard laboratory methods for all applicable water quality analyses as presented in Table 10 Lake Elsinore and Canyon Lake Monitoring Programs Samples will be analyzed for total N and total P soluble reactive SRP NO3 N NO2 N NH4 N chlorophyll a TDS and other constituents Tables 3 and 4 Organic N and total inorganic N TIN concentrations will be calculated from the measured N forms as presented in Table 11 Unfiltered water samples will be digested for total N and total P using persulfate methods 4500 N and 4500 1998 SRP NOs N NO N NH 4 N concentrations will be determined on samples filtered through 0 45 u polycarbonate syringe filters and acidified with H2SO 4 nutrient samples will be analyzed colorimetrically on an Alpkem Autoanalyzer or equivalent following standard methods APHA 1998 Specifically dissolved and total P will be determined using the ascorbic acid reduction method 4500 P G total N and NO3 N NO2 N will be measured using the cadmium reduction flow injection method 4500 NO F and NH4 N levels will be quantified using an automated phenate method
207. e 50 g sodium potassium tartrate in 400 mL ammonia free deionized water and dilute to about 500 mL Add 3 to 5 pellets of sodium hydroxide Boil the solution with stirring for at least 1 hour to drive off ammonia contamination Add make up water if needed Cover the flask and cool to room temperature Add acid dropwise sulfuric or hydrochloric about 5 normal to reach a pH of 7 5 0 4 Dilute to 500 mL 8 10 4 Store in the refrigerator up to six months 8 11 Stock buffer solution 8 11 1 Sodium phosphate dibasic anhydrous Na2HPOA 67 g 8 11 2 Sodium hydroxide 10 g 8 11 3 Dilute to 500 mL with DI water 8 11 4 Dissolve 67 g sodium phosphate dibasic anhydrous Na2HPO4 or 127 g sodium phosphate dibasic heptahydrate Na2HPO4 7H20 in about 350 mL ammonia free water Add 10 0 g sodium hydroxide and stir to dissolve Dilute to 500 mL 8 11 5 Store at room temperature for up to six months 8 12 Working buffer solution 8 12 1 10 Sodium potassium tartrate solution above 240 mL 8 12 2 Stock buffer solution above 100 mL 8 12 3 10 Sodium hydroxide stock solution above 160 mL 8 12 4 Dilute to 500 mL with DI water 8 12 5 Combine reagents in the stated order add 100 mL stock buffer solution to 2401 or 250 mL 10 sodium potassium tartrate solution and mix Add 10 sodium hydroxide stock solution Dilute to 500 mL and invert to mix 8 12 6 Store at room temperature for up to six months 8 13 Alkaline sodium salicyla
208. e LCS must be homogenized If samples are filtered a LCS must be filtered LCS readings must be inside historical acceptance limits 10 2 MB A method blank is analyzed every 20 samples per matrix type or once per batch whichever is greater The method blank must be less but not more negative than 0 7ppm for liquid samples and 0 3ppm for water samples If samples are homogenized the blank must be homogenized If samples are filtered a blank must be filtered Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured raw concentration of the sample Sample results below the reporting limit are considered to be ND Revision 5 0 26 Page 8 of 9 and will not require a note however method blank results must not be more negative than the reporting limit 10 3 MS MSD A matrix spike and matrix spike duplicate is analyzed every 20 samples per matrix type or once per batch whichever is greater Take 20 mls of the sample and add 40ul of the 2000mg L intermediate std into a TOC vial Upon analysis the result must fit within an 80 to 120 window true value 4 0mg L and have a RPD no greater than 10 10 4 See section 8 5 2 for solid QC requirements 10 5 Inorganic Carbon Purge Blank A blank made from sodium carbonate is acidified and purged exactly as a sample would be processed to ensure that all inorganic carbon is being adequately removed
209. e Malathion Parathion TEPP EPN Monocrotophos Sulfotepp SPM 844 Azinphos Ethyl Dioxathion Leptophos Phosphamidon Carbophenothion Ethion Phosmet Terbuphos Chlorfenvinphos Famphur SPM 854 Aspon Dichlofenthion Fenitrothion Thionazin Chlorpyrifos MethylDicrotophos Fonofos Trichlorfon Crotoxyphos Revision 4 1 Page 7 of 16 7 4 4 O53 8141 EPA 1176A Atrazine NPM 107A Simzine 7 4 3 1 Intermediate Calibration Standard Dilute the following amounts to 10mL with MtBE in a 10mL volumetric flask Ultra Stock Amount Intermediate Concentration Concentration ppm mL ppm SPM 824 200 2 0 40 SPM 834 200 2 0 40 SPM 844 200 2 0 40 SPM 854 200 2 0 40 EPA 1176A 1000 0 4 40 NPM 107A 1000 0 4 40 7 4 3 2 Working Calibration Standard Seven Calibration Standards are made by diluting the following amounts of 40ppm Intermediate Standard in autosampler vials as follows Working Amount of Amount of Concentration Intermediate MtBE ppm uL uL 0 8 20 960 2 0 50 930 4 0 100 880 5 0 125 855 7 0 175 805 8 0 200 780 10 0 250 730 Add 20uL of 250ppm surrogate standard 5ppm and 8uL of 500ppm internal standard 4ppm to each calibration standard 7 4 3 3 Reporting Limit Standard Dilute 20uL of 40ppm Intermediate Standard into 960uL of MtBE for a final concentration of 0 8ppm Also add 20uL of 250ppm surrogate standard and 8uL of 500ppm internal standard 7 4 3 4 Continuing Calibration Verification Standa
210. e Program Administrator for the SJRIPP shall maintain these records until 2030 The SJR Component Program Administrator shall maintain copies of all reports and have access to all monitoring program sample collection records sample transport records chain of custody and field analysis forms and all records submitted by contract laboratories associated with the CL and SJW Monitoring Programs As per the grant agreement the Program Administrator for the SJR Component Program shall maintain these data until completion of the grant At that time the SJR Component Program Administrator will turn those records over to the TASK FORCE Monitoring Program Manager All records will be passed to the Santa Ana Regional Board TMDL Program Manager Santa Ana Regional Board Grant Program Manager and or other State Agencies as required and appropriate for each project at project completion Copies of the chemical monitoring records will be maintained by LESJWA and each laboratory contracted by the TASK FORCE for five years after project completion then discarded except for the database which will be maintained without discarding Copies of other monitoring records will be maintained by the Program Administrator for the Project for five years after project completion then discarded Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 24 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE B1 SAMPLING PROCESS DESIGN Sample collection points for each
211. e batch in ex IC WATERTEMP click Save and then click Cancel back in Data Entry Review 13 4 Process Transfer Batch PeakNet Main Menu Batch Processing Input Select the Input tab Click Select to acquire a complete schedule of samples to send or click Build to select individual data files 1f Build 1s selected the file will need to be saved as a new file name do not save as an existing file name Also in the Input tab under Process Methods click the circle next to From Schedule Once you have selected or created a schedule click the Export tab and there click Browse to select a file name ex WATERS in which to save the data to send to Data Tool and click Save Also in the Export tab select a report type by clicking the circle next to Full report type When finished click OK at the bottom of the Processing window Then click the Start icon looks like an arrow circling clockwise or under the Processing menu select Start This sends the data to Data Tool 13 5 Merge Files in Element DataTool and make edits Element Laboratory Data Tool Main In Data Tool under Element Data Entry Table click Browse Select the Element User File that was created above ex IC WATERTEMP and click Open Under Instrument Data Files click Browse Click Clear to remove previous work From the bottom right box double click the file exported from PeakNet Batch ex WATER the samples will appear in the top left box Highlight the desired samples click Include a
212. e memory interference effects Gold is added to the internal standard spiking solution to address this concern Silver is only slightly soluble in the presence of chloride unless there is sufficient chloride concentration to form the soluble chloride complex Therefore low recoveries of silver may occur in samples fortified sample matrices and even fortified blanks if determined as a dissolved analyte or by direct analysis where the sample has not been processed using the total recoverable mixed acid digestion HCl acid is added to all silver AAR and digests to address this issue The total recoverable sample digestion procedure given in this method will solubilize and hold in solution only minimal concentrations of barium in the presence of free sulfate For the analysis of barium in samples having varying and unknown concentrations of sulfate analysis is completed as soon as possible after sample preparation This method should be used by analysts experienced in the use of inductively coupled plasma mass spectrometry ICP MS the interpretation of spectral and Revision 3 0 M12 200 8 Page 3 of 26 matrix interferences and procedures for their correction ESB personnel are to be trained by the Metal Section Leader or the Laboratory Director 1 10 Our laboratory has on file the required initial demonstration performance data described in Section 9 2 that was generated prior to using the method for analysis 2 SUMMARY OF METHOD
213. e potential hazards to both the analyst and the environment involved 2 2 A chemical inventory is maintained in order to monitor that chemical volumes are kept to a minimum Whenever supplies are ordered the smallest quantity needed is purchased Quantities are based on expected usage during shelf life 2 3 Actual reagent preparation volumes are based on anticipated usage and reagent stability It is the laboratory s responsibility to comply with all federal state and local regulations governing waste management particularly the hazardous waste identification rules and land disposal restrictions The laboratory has the responsibility to protect the air water and land by minimizing and controlling releases from fume hoods and bench operations The laboratory must attempt to comply with the letter and spirit of sewer discharge permits and regulations and with all solid and hazardous waste regulations particularly the hazardous waste identification rules and land disposal Excess reagents samples digests and extractions are characterized and disposed of in an acceptable manner 4 1 Acid and alkaline wastes are neutralized prior to sewer disposal More concentrated acid and base solutions are hauled away by an independent waste hauler See SOP S05 4 2 Waste generated from the Chemical Oxygen Demand analysis containing chromate mercury and silver is poured into a COD Only drum which is hauled away by an independent waste hauler 4 3 W
214. e results are used to prepare a calibration curve for each analyte During this procedure retention times must be recorded 9 4 The calibration curve is verified on each working day prior to sample analysis after every 10 samples at the end of the run The IPC an Instrument Performance Check is essentially equivalent to the ICV CCV required in other methods If the response for any analyte varies from the expected values by more than 10 the test must be repeated using fresh calibration standards If the results are still out of range a new calibration curve must be prepared for that analyte and results that are not bracketed by working QC must be qualified or reanalyzed f the retention time for any analyte varies outside the curtain window reset the retention time to the current CCV value and reprocess the run 9 5 Standard Concentrations and Recipes 9 5 1 ICV IPC Standard Initial Calibration Verification Instrument Performance Check Analyte Conc Acceptance Range Cl 50 90 110 50ppm 90 110 SO 50 90 110 9 5 2 CCV IPC Standards For recipes see Calibration Standard 5 and 8 Analyte Conc Acceptance Range Mid High Revision 7 0 119 Anions Page 7 of 15 Cl 50 250ppm 90 110 NO 50 100ppm 90 110 SO 50 250ppm 90 110 9 5 3 Low level Check Standards 9 5 3 Low Level CCV Standard 3 A low level CCV Chloride Nitrate and Sulfate all at 20ppm is analyzed at the end of e
215. e the blank source for possible contamination If the above does not correct the problem remake the method blank carefully to be certain that the procedure is followed correctly A new MB may be considered as part of the original batch as long as 24 hours has not been exceeded from the start of processing of the first sample and the start of processing of the new MB If a new MB is processed conditions must be identical to those conditions under which the samples were prepared and analyzed Wherever possible the analyst must rerun samples associated with an invalid method blank result Invalid blanks must be accompanied with the qualifier QBLK Report results that management deems acceptable Sample results above the reporting limit must be accompanied with the proper qualifier NBLK if the method blank associated with the sample 2 7 1 exceeds a concentration greater than 1 10 of the measured raw concentration of the sample The raw concentration is the value prior to dilution or concentration factor 2 7 2 does not satisfy method requirements if stricter see SOP Note The blank value noted in the NBLK qualifier is the raw blank result If the sample being qualified was diluted in addition to NBLK the analyst must also attach the qualifier NBLKd which includes the sample raw result Note Method blank results below batch acceptance criteria i e RL or 2 RL are considered to be ND and will not require a note If batch ac
216. ection The field data completed goal for data collected under this program is 90 percent Laboratory Data Laboratory data completeness is a quantitative measure of the percentage of valid data for all analytical data as determined by the precision accuracy and holding time criteria evaluation The laboratory completed goal for data collected under this program is 90 percent It may not be possible to meet the target for completeness in certain situations for example during a severely dry year when not enough rain falls during storms to create a sampleable condition In these situations the TMDL Program Manager or QA Program Manager will be consulted for guidance and a description of efforts made to meet the completeness target will be provided in the Annual Report Representativeness Representativeness is a qualitative expression of the degree to which sample data accurately and precisely represent a characteristic of a population a sampling point or an environmental condition Representativeness is maximized by ensuring that for a given task the number and location of sampling points and the sample collection and analysis techniques are appropriate for the specific investigation and that the sampling and analysis program provides information that reflects true site conditions Field Data Representativeness of field data is dependent upon the proper design of the data collection procedures Representativeness of the field data wil
217. ed within the method which may include mass spectral tuning second column confirmation ICP inter element interference checks chromatography retention time windows sample blanks spectrochemical absorption or electrode response factors Approved by Susann K Thomas Date 08 28 06 Revision 7 0 006 Page 1 of 11 CORRECTIVE ACTION FOR CHEMICAL ANALYSIS Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE Effective Date 09 08 06 The following is a description of Edward S Babcock amp Sons Corrective Action Protocol for quality control samples Please consult the analytical SOP for method specific requirements that may supercede the requirements below After following these procedures if it is still unclear how to proceed discuss the problem with the supervisor or QA Manager 1 0 Laboratory Control Laboratory Fortified Blank Blank Spike 1 1 When a LCS is out of the laboratory acceptance criteria the batch is considered to be out of control 1 1 1 Recheck the calibration This may be done with the analysis of a QC sample from a third source If the standard shows the calibration to be off recalibrate or restandardize depending upon the method and rerun samples For instrumental analyses check for instrument setup problems Check blanks to determine if there is contamination in either the glassware or reagents N 1 2 Ifthe above does not correct the problem remake the laboratory control
218. ed if proceeded by a sample of elevated concentration 250 mg L for and SO 100 mg L for NO3 to eliminate possible carry over contamination 11 9 Ifthe resulting chromatogram fails to produce adequate resolution or if identification of specific anions is questionable fortify the sample with an appropriate amount of standard and reanalyze Revision 7 0 I19 Anions Page 13 of 15 11 10 Wherever possible evaluate coeluding peaks by redrawing the baseline rather than sample dilution and document on your raw data 11 11 The following extraction should be used for solid materials Add an amount of reagent water equal to ten times the weight of solid material taken as a sample This mixture is agitated for sixty minutes by shaking intermittently Filter the resulting slurry before injecting using a 0 20 micron membrane type filter This can be the type that attaches directly to the end of the syringe A sample is duplicated for every batch prepared 12 0 Calculation 12 1 Prepare separate calibration curves for each anion of interest by plotting peak size in area or peak height units of standards against concentration values The system will then compute sample concentration by comparing sample peak response with the standard curve 12 2 Report results in mg L 12 3 Report NO as N NO as N or as NO if desired by the client 4 12 4 Dilutions Raw results are displayed on the chromatograms Dilutions are
219. ell by inverting several times before placing in the Optical Well for reading will be 7 2 2Keep the outside surface of the cell clean and dry Apply a drop of silicone oil to the outside and wipe with a cloth or tissue Finish with a chem wipe 7 2 3When placing any standards in the well always use the light shield to cover the well in order to keep out ambient light 7 3Carry out the following steps lFirst place a cell of NANOPURE water in the dieu Ted dada dad J WwW cell holder 2Press the CAL key 3Press ENTER 4The instrument will advance to the next standard display the expected value and the S1 light 5Place the 20 NTU standard in the cell holder 6Press ENTER Revision 45 0 Page 5 of 7 9 0 Note 7 3 70nce the instrument displays the next standard value and Sf light place that standard in the cell holder I36 Turbidity press ENTER and so on until all the standards have been read 7 3 8The standard values are 20 200 1000 and 4000 7 3 9After t he last standard is processed press the CAL key 7 4 Analysis 7 4 1 Clean and rinse the cell with Nanopure wiping all excess water from the sides with Apply a drop of silicone oil to the tissue outside Finish and wipe with a cloth or tissue with a chem wipe Never handle the cell where the light strikes 7 4 2 Check the calibration by reading the 0 8 Lab Control
220. eness criteria of 90 are met The sources of variability include storm sizes quantity of the stream flow part of the hydrograph sampled seasonality topography and land use The sampling program addressed the spatial and temporal variability by selecting sampling locations representing different land use types and by collecting multiple samples at one site 8 to 12 across the hydrograph and 12 samples at each lake station The potential bias of the watershed sampling could be missing the rising limb or the peak of the hydrograph This bias is addressed by sampling three storms at each site and examining the data to make sure they are consistent with historical data During data reduction statistical analysis will be conducted to determine the variance and confidence level Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 25 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE B2 SAMPLING METHODS REQUIREMENTS San Jacinto Watershed Nutrient TMDL Monitoring Program Details of this program element can be found in the Appendix D Lake Elsinore Canyon Lake TMDL Compliance Program San Jacinto River Watershed Sampling Plan following the sampling methods presented in Table 8 Lake Elsinore Nutrient TMDL Monitoring Program In situ water column properties temperature DO electrical conductivity pH turbidity and redox potential will be measured at 1 m intervals using a Hydrolab DataSonde 4a and Surveyor 4 or equivalent wh
221. entration must not exceed its verified linear range In these circumstances analyte detection limits are raised and determination by another approved test procedure that is either more sensitive and or interference free is recommended 11 4 8 Report data as directed in Section 12 11 5 Our laboratory uses the internal standard technique as an alternate to the method of standard addition by adding one or more elements not in the samples and verified not to cause an uncorrected interelement spectral interference at the same concentration which is sufficient for optimum precision to the prepared samples blanks and standards that are affected the same as the analytes by the sample matrix The ratio of analyte signal to the internal standard signal is used for calibration and quantitation This technique is very useful in overcoming matrix interferences especially in high solids matrices The analyst monitors internal standard response for large drops that might indicate improper spiking of La or sample matrix interference 12 0 DATA ANALYSIS AND CALCULATIONS 12 1 Sample data should be reported in units of ug L for aqueous samples 12 2 For dissolved aqueous analytes report the data generated directly from the instrument with allowance for sample dilution Do not report analyte concentrations below the MDL 12 3 For total recoverable aqueous analytes most results are reported directly from the instrument readout since normal digestion dilutio
222. ep dilution correct on bench sheet if necessary 12 7 2 3 2 Check if source sample is greater than four times the BS value If it is Qualify the MS MSD QM 4X Revision 4 1 M07 200 7 Page 19 of 21 12 7 2 3 3 If only one spike is out and the RPD is less than twenty and if there are ten or less analytes you can make the red spike the MSD and use the qualifier QMSDr 12 7 2 3 4 QFnt If the source sample does not require the reporting of the analyte 12 7 2 3 5 QOcal if result is over LDR 12 7 2 4 Verify dilutions on prep sheet and in lims 12 7 2 5 Samples diluted that result in an answer of ND or J flag N RLm 12 7 2 6 Right click Sort by analyte order 12 7 2 6 1 Check ND results for any negatives greater than RL 12 7 2 6 2 If a blank has been qualified check for any analytes less than 10 times the blank result This result may be passable if it is ND if it is not it must be RE d and Qualified SUS or qualified NBLK The result may be reported if it is 1Ox greater than the blank result The re s should be addressed now in Project Management update status Edit comment create bench sheets if necessary 12 7 2 6 3 Check for results over the LDR these need to be RE d entered as 9999 and qualified SUS NOcal 12 7 2 7 Sort by Sample ID 12 7 2 7 1 Calculate any sodium percentage or SAR s 12 7 2 7 2 Highlight page right click custom status update to peer review 12 7 2 7 3 Save Ok Done 12 7 3 Fill out peer
223. ermined similarly to phosphorus reacting with molybdate reagent to produce a blue color and should be considered when present in concentrations higher than phosphorus Concentrations as low as 0 1mg As L can interfere 5 3 Hexavalent chromium and nitrite interfere to give results about 3 lower at concentrations of 1mg L and 10 15 lower at 10mg L 6 0 Safety Safety glasses and gloves must be worn when dealing with acid digests Revision 5 0 I42 Page 3 of10 See SOP S01 Concentrated Acids and Bases SOP 503 Spill Control Policy 7 0 Equipment JNN ecl 2 3 4 Hot plate 100m1 beakers Watch glass Spectrophotometer Spectronic Genesys 10uv and Spectronic 20D set at 880nm 8 0 Glassware Preparation 8 1 Glassware is stored separately for Total Phosphorus and Orthro Phosphate phosphorus use only 8 2 All glassware is acid washed in 1 1 HCl immediately after use followed by thorough rinsing with three portions of D I water If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final Des rinse 9 0Phosphate Reagents and Standards 9 1 Reagent water Nanopure 9 2 9 2 1Ascorbic Acid solution Dissolve 0 539 Ascorbic acid in 30m1 Nanopure water Make fresh bef
224. ery Work Status and then print 3 1 1 Inorganics Inorganics and Soil ag 3 1 2 Microbiology Bateriological 3 2 Pick up reviewable list from printer Revision 4 0 Q10 Page 3 of 6 3 3 Pull up each sample report in Data Entry Review by work order under Laboratory and review on screen 3 4 Examine also the report Click on the printer button Choose a data review format e g rev InorgSuperRev ppt Click preview button to view report 3 5 Data is examined for the following tests have answers The correct units and reporting limits are entered Customers name and sample ID make sense with the answers Qualifiers are appropriate Answers relate to each other properly For intra sample quality control the following procedures for checking correctness of analyses are applicable to water samples for which relatively complete analyses are made These include pH conductivity total dissolved solids TDS major cationic and anionic constituents demand parameters nutrients and trace organic contaminants Use the criteria below 3 5 6 Calculations are correct The following calculations appear on the last pages of the report in the Inorganic Supervisor Review Aggressive Index Langlier Index Total Anions and Electrochemical Balance Other calculations must be manually calculated such as TDS by summation carbon dioxide chloramines Cr3 and any total inorganic or organic nitrogen that did not have Calc in their name
225. es per matrix type or one per batch whichever is more The relative percent difference is calculated for the duplicate samples run as follows ABS Run 1 Run 2 Run 1 Run2 2 Duplicates must be within a maximum RPD of 20 12 3 A laboratory control standard is analyzed every 20 samples or once per batch whichever is more and reported for every matrix type The laboratory control is compared to acceptance ranges generated from in house historical data The method target range for historical Limits is 85 115 based on a series of Laboratory studies which gave the following results For the 300 mg L mixed primary standard the average 5 d BOD was 198 mg L with a standard deviation of 30 5 mg L Lab control standards outside the acceptance range cause the analysis to be put into question Troubleshooting must be performed to attempt to identify the problem The Winkler LCS may be used to accept a sample batch The Supervisor QA Manager or Laboratory Technical Director is consulted to determine if data is still reportable If data is reported in a batch without an acceptable LCS all client reports must be flagged with NLbod See ESB SOP Q06 for more details 12 4 Probe Blank An unseeded blank is analyzed with each batch to monitor probe performance Target range should read 0 4 mg L 12 5 An MDL study is completed whenever major equipment or procedural changes are made A standard Glucose Glutamic Acid solution is prepared
226. ether as a group An analytical batch can include prepared samples originating from various environmental matrices and can exceed twenty samples 11 0 Calculation of QC Results 11 1 Convert results into final units prior to calculation 11 2 Always use the maximum number of digits to calculate QC results percent recovery RPD etc 11 3 QC results may round up to be acceptable For example If 9596 is the lower limit acceptance criteria 11 3 1 294 696 is acceptable 11 3 2 94 5906 is not acceptable Approved by Susann K Thomas Date 08 28 06 Revision 2 0 S07 Page 1 of 2 1 0 2 0 3 0 4 0 Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE Pollution Prevention and Waste Management Effective Date 09 08 06 Pollution prevention encompasses any technique that reduces or eliminates the quantity and or toxicity of waste at the point of generation Numerous opportunities for pollution prevention exist in laboratory operation The EPA has established a preferred hierarchy of environmental management techniques that places pollution prevention as the management option of first choice Whenever feasible laboratory personnel will use pollution prevention techniques to address their waste generation In some cases when wastes cannot be feasibly reduced at the source recycling is utilized Chemical Volume Reduction 2 Wherever permitted methods are used that require smaller volumes of reagents thereby reducing th
227. ethod covers the determination of ortho phosphate phosphorus in drinking surface and saline waters domestic and industrial wastes 1 1 Health Effects of Phosphorus 1 1 1Too much phosphate can cause health problems Such as kidney damage and osteoporosis While burning white phosphorus may cause damage to the liver the heart or the kidneys 1 2 Environmental Effects of Phosphorus 1 2 1In water white phosphorus will accumulate in the bodies of aquatic organisms In soil phosphorus will remain for several days but in deep soils and the bottom of rivers and lakes phosphorus will remain for a thousand years or so Orthophosphates applied to agricultural or residential cultivated land as fertilizers are carried into surface waters with storm runoff 1 2 2The increasing phosphorus concentrations in surface waters raises the growth of phosphate dependent organisms such as algae and duckweed These organisms use great amounts of oxygen and prevent sunlight from entering the water This is known as eutrophication Revision 5 0 I27 OP Page 2 of 9 2 0 Working Range 0 05 1 0mg L 3 0 Summary Ammonium molybdate and antimony potassium tartrate reacts in an acid medium with dilute solutions of phosphorus to form an antimony phospho molybdate complex This complex is reduced to an intensely blue colored complex by ascorbic acid The color is proportional to the phosphorus con
228. eting standards must meet the calibration verification criteria When a calibration verification standard fails to meet the QC criteria all samples that were injected after the last standard that last met the QC criteria must be evaluated to prevent misquantitations and possible false negative results and re injection of the sample extracts may be required However if the standard analyzed after a group of samples exhibits a response for an analyte that is above the acceptance limit i e gt 1596 and the analyte was not reportable in the specific samples analyzed during the analytical shift then the extracts for those samples do not need to be reanalyzed as the verification standard has demonstrated that the analyte would have been detected were it present If the analyte was reportable then the sample must be reanalyzed or qualified In contrast if the standard analyzed after a group of samples exhibits a response for an analyte that is below the acceptance limit ND results may be accepted if the RL check response is greater than the MB response Reportable results must be reanalyzed or qualified Sample injections may continue for as long as the calibration verification standards and standards interspersed with the samples meet instrument QC requirements If the peak response is less than 2 5 times the baseline noise level the validity of the quantitative result may be questionable The analyst should consult with the source of the sample t
229. ever method blanks however with low surrogate recoveries may indicate a problem Please consult your supervisor 7 0 Internal Standard 7 1 When internal standard performance is outside method specified criteria the sample chromatogram is examined for possible interferences and the extract is reinjected if necessary 7 1 Ifthe reinjected result is compliant results are reported from the second injection 7 1 2 re injection does not produce compliant results a calibration check is injected or the internal standard performance of the closest calibration check sample is examined 7 1 2 1 If the calibration check internal standard is valid the sample is reextracted if sample is available 7 1 2 2 If the calibration check internal standard is not valid the instrument must be recalibrated and all samples not bracketed by working QC must be reanalyzed 7 2 If re extraction is not possible or it does not correct the problem the appropriate qualifier NIS must be placed on the client s report for samples that management deems reportable 8 0 Carry Over 8 1 If during the course of an analysis a sample is analyzed containing elevated levels of the analyte of interest the analyst must reanalyze samples with a result falling between the reporting limit and ten times the reporting limit that followed the contaminating sample If the sample will be reported on a J flag report all results greater than the MDL must be evaluated f
230. f 8 preserved sample over a pH strip Place a S on the Work Order Printout and sample If the sample is not lt 2 add more H2SO0 and repeat the above steps until the sample is lt 2 See section 3 5 9 0 Oil and Grease O amp G 9 1 Oil and grease samples must be sampled in glass If they are not sampled in glass a note is placed in analyte comments Preserve samples with approximately 1ml of 1 1 sulfuric acid per 500 mL jar of sample to pH lt 2 Dip strip into jar to check pH Place an S O G on the Work Order Printout and sample 10 0 Total Petroleum Hydrocarbons TPH 10 1 Total Petroleum Hydrocarbons samples must be sampled in glass Preserve samples with approximately 1 2 ml of 1 1 sulfuric acid per 1L jar of sample to pH 2 Place an S TPH on the Work Order Printout and sample 11 0 Oxyhalides chlorate chlorite bromate 11 1 Add 0 15 mL 3 drops of 35 EDA solution per quart bottle or 2 drops per pint Place an E on the Work Order Printout and sample 11 1 1 Note A sample for bromide only does not require preservation however it may be analyzed on the preserved sample 11 1 2 35 Solution EDA Dilute 35ml pharmaceutical grade anhydrous to 100ml D I Store at room temperature make fresh monthly 12 0 Total Organic Carbon TOC 12 1 Preserve samples with approximately 0 1 ml of 1 1 sulfuric acid per 43 mL amber vial to pH 2 Place a S on the Work Order Printout and sample 13 0 O
231. f the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 7 0 Reagents and Standards 7 Stock potassium acid phthalate potassium biphthalate or potassium Hydrogen Phthalate Revision 5 0 Page 3 of 7 7 1 1 I07 COD Draft LCS MS Intermediate Standard Dissolve 0 425g in Nanopure water and dilute to 1 liter 1 mL 250 mg L COD 0 2ml 50mg L COD Store LCS solution in the refrigerator in an amber bottle for up to 3 months 7 1 1 1 Midlevel LCS 250 ppm 1 mL of above intermediate and 1 mL Nanopure into COD vial made fresh each run 7 1 1 2 High Level LCS 500ppm 2 mLs of above intermediate into COD vial made fresh each run High CCV 7 1 1 3 Working MS 125 ppm 0 5 mL of above intermediate 0 5 mL of Nanopure and 1 mL sample into COD vial made fresh each run Calibration Intermediate Standard Follow above procedure using a second source of potassium acid phthalate Store STD Intermediate in the refrigerator in amber bottles for up to 3 months 7 1 2 1 Dilute Intermediate Standard further to create a seven point curve 7 1 2 2 Single point calibrator 250 ppm 1 mL of 500ppm non LCS intermediate made fresh when recalibration is necessary and 1 mL Nanopure into COD vial 7 2 Digestion Solution purchased premade reagent from HACH Vials are stored at room temperature until manufacturer s specified holding time 7 3 Reagen
232. face waters and solids 10 1 Liquids and semi solids 10 1 1 Generally a multiple dilution or serial dilution is used on non drinking water which may contain high amounts of bacteria A series of dilutions are needed in order to calculate the most probable number of bacteria per 10 1 2 100 mL MPN 100mL 10 1 1 1 10 mL portions of sample are inoculated into the first 5 broth tubes 10 1 1 2 Ten mL of sample is then transferred into 90 mL of sterile dilution water This dilution represents 1 mL of sample per 10 mL aliquot of solution Five 10 mL portions of this first dilution are inoculated into the following five broth tubes 10 1 1 3 IO mL of the first dilution are transferred into 90 mL of sterile dilution water This second dilution represents 0 1 mL of sample per 10 mL aliquot of solution Five 10 mL portions of this second dilution are inoculated into the third set of five broth tubes If the sample is cloudy or contains a small amount of dirt a third dilution may be considered If the sample is very dirty additional dilutions will be needed Raw liquid influents are generally diluted to 1x10 mL at the beginning of the series and ending at 1x10 mL Semi solid raw influents usually are started at 1x10 mL and end at 1x108 mL 990 mL and 999 mL dilution bottles may be used for these higher dilutions Revision 6 0 B02 MTF Page 5 of 9 10 2 Solids 10 2 1 If a sample is solid generally 10 grams is used to ensure
233. fference RPD of each duplicate analysis will be calculated and compared to control limits The RPD is calculated as follows ABS Run 1 Run 2 RPD X 100 Run 1 Run 2 2 A maximum of 20 is allowed 12 2 The reading of the KCL standard is used in the following calculation section 13 1 to establish the calculation factor 12 3 The second source of KCl is used as a lab control and calibration check It is analyzed at two different concentrations at the beginning of the analysis every 20 samples per matrix type and at the end of the run 12 3 1 If the percent recovery does not fall within the control limits 90 110 the analysis is considered to be out of control The problem must be corrected before th analysis can proceed 12 4 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration of Revision 5 0 I14 EC Page 6 of 7 1413umhos cm The average percent recovery must be 80 120 with a maximum RSD of 10 12 5 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet labora
234. ficant change A new MDL study is required unless the new column proves to be more sensitive than its confirmation column A second instrument of the same type will be compared to the original instrument by analysis of a RL standard If the sensitivity of the new instrument is the same or better than the sensitivity of the old instrument a MDL study is not necessary If it is not as sensitive a MDL study will be performed on the new instrument If an instrument is torn down and moved the RL standard after the move will be compared to the RL standard prior to the move If it is not as sensitive a MDL study will be performed on the instrument once it is up and running in the new location Sensitivity is measured by comparing the signal to noise ratio of an analyte in one RL standard versus another The RL standard with the higher S N ratio demonstrates a system that is more sensitive 4 2 Standards are generally spiked at or near the reporting limit 2 5 5 times the estimated MDL per Appendix B of 40CFR 136 or at a method prescribed level into a quality system matrix free of target analytes or interferences A minimum of seven replicates are carried thru all sample processing steps of the analytical method See QA Manual for calculation If the procedure for solid and sludge matrices is identical except for initial volume the study is Revision 7 0 Q01 Page 11 of 14 4 3 44 4 5 4 6 4 7 4 8 performed using solid prepara
235. foam on the top and the Durham tube sounds hollow If CO formation is observed in the EC tube and the tube fluoresces in UV light the sample is considered positive for E coli Any tube that is positive for fecal coliform bacteria or E coli must also be positive for total coliform bacteria Revision 6 0 Page 6 of 9 B02 MTF 12 0 Quality Control Note See also ESB SOP for general QC requirements 12 1 Positive and Negative controls 12 1 1 12 1 2 12 1 3 To check for the possible occurrence of false positives due to fecal water bath malfunction during a fecal coliform test one EC fermentation tube is inoculated with Enterobacter aerogenes Another tube is inoculated with Pseudomonas aeruginosa They are incubated for 24 2 hours If the fecal water bath has maintained a constant temperature of 44 5 C 0 2 C the E aerogenes and P aeruginosa will no longer be viable and will not produce gas As an additional fecal water bath QC check another EC fermentation tube is inoculated with Escherichia coli and is incubated for 24 2 hours If the water bath temperature has been properly maintained the E coli will produce gas A fourth tube of EC media is incubated It is a blank to ensure sterility 12 2 Duplicates 12 2 1 12 2 2 12 2 3 On a monthly basis each analyst shall make parallel analyses of at least one positive sample Sample duplicates are performed at a frequency of 596 or once per batch
236. for acceptance criteria analytes outside original method criteria must be qualified as specified below 4 5 4 2 1 All samples with results at or above the reporting limit are flagged with a qualifier signifying a low or high bias on specific analytes NCALI or NCALh 4 5 4 2 2 Samples that are ND for specific analytes 4 5 4 2 2 1 If the ICV is bias high a qualifier is not necessary Revision 7 0 006 Page 7 of 11 4 5 4 2 2 2 If the ICV bias 15 low and the reporting limit standard analyzed at the end of the run or batch of 20 samples shows a signal 4 5 4 2 2 2 1 greater than the method blank then results do not require a qualifier 4 5 4 2 2 2 2 less than the method blank then results may not be reported and sample analysis must be repeated after the system has been brought under control If reanalysis is not possible then results are reported with the NCALI qualifier and the RL is raised to the level of the ICV 4 5 5 If any one or more analytes are outside laboratory acceptance criteria for two consecutive batches a follow up must be performed to determine the cause See method SOP for specific exceptions 5 0 Continuing Calibration Checks 5 1 92 5 3 54 If a calibration check CCV falls outside the acceptance criteria it must be reanalyzed immediately If it is still out of range determine the cause of the problem Make necessary corrections and perform either two consecutive successful calibratio
237. forms included as Attachments 1 and 2 Analytical samples will be transferred to the laboratory under required Chain of Custody procedures using a standard Chain of Custody form included as Attachment 3 laboratory and field measurement data submitted to SAWPA for inclusion in the SAWDMS database will follow guidelines and formats established by SWAMP http www waterboards ca gov swamp qapp html Data transmitted to SAWPA in a standard electronic format and uploaded to the database through batch set electronic means All contract laboratories will maintain a record of transferred records and will periodically assess their record of transferred records against those actually held by the TASK FORCE Prior to upload QA QC tools will check new data against existing data in the database for completeness validity of analytical methods validity of sample locations validity of sample dates and data outliers Data not passing QA QC tests will be returned to the originating laboratory or generator for clarification and or correction When all data within a batch set have passed QA QC the data will be uploaded to the database A unique batch number date loaded originating laboratory and the person who loaded the data will be recorded in the database so that data can be identified and removed in the future if necessary The TASK FORCE s database is backed up using built in software backup procedures In addition all data files will be backed
238. frigerated at 4 prior to analysis 6 2 The maximum holding time prior to BOD incubation is 48 hours CFR part 136 Since even a short time can significantly change the BOD results the sample is set up for incubation as soon as possible after the sample has been taken Interferences 7 Adjusting the temperature of the dilution water to 20 prior to use is important for reproducible results Revision 5 0 I05 BOD Page 2 of 8 7 2 Any chemical present in the sample that 1s detrimental to the seed bacteria would cause a negative interference i e chlorine acid or alkaline 7 3 See SOP 124 for interferences affecting the dissolved oxygen measurement Safety Issues Some of the reagents used in the analysis are corrosive Proper care must be taken to prevent contact The use of gloves and safety glasses are essential when performing this test See SOP S01 Concentrated Acids and Bases SOP S03 Spill Control Policy Instrumentation Equipment 9 1 Incubator with temperature setting at 20 1 C excluding all light to prevent the possibility of photosynthetic production of dissolved oxygen 9 2 300 ml capacity bottles with ground glass stoppers 9 3 Plastic cup covers 9 4 Dissolved Oxygen Probe see 124 9 5 General laboratory glassware pipets graduated cylinders Note All glassware is cleaned immediately after use by thorough rinsing with three portions of D I water If glassware st
239. from the samples The blank must be below the reporting limit or steps should be taken to determine the presence if inorganic carbon 10 6 The instrument is set to report an average of several injections Repeat injections until consecutive peaks are obtained that are reproducible to within a maximum coefficient of variation CV of 10 or a standard deviation SD of the area counts less than 200 10 7 See section 8 5 2 for solid QC information 10 8 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit 10 8 1 LOD Verification On a yearly basis a QC sample is spiked at a level of not more than 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL 10 9 Demonstration of Capability Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 10 10 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four conse
240. g kg Run Data multiplier 1 misc 1 units mg kg Revision 4 1 53 8141 Page 15 of 16 So that data in the run can display the final result the multiplier is used to account for the preparation concentration Since LIMS will apply the concentration factor again based on the initial and final volumes the miscellaneous field takes the multiplier back out before data is transferred to LIMS Since the miscellaneous field also affects RL s and MDL s the analyst must manually adjust these limits back in the LIMS by multiplying the solid limits by 0 333 14 0 CORRECTIVE ACTION FOR OUT OF CONTROL UNACCEPTABLE DATA 14 1 SOP Q06 Corrective Action 15 0 POLLUTION PREVENTION AND WASTE MANAGEMENT 15 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP 507 Pollution Prevention 16 0 METHOD PERFORMANCE 16 1 See Method 8141 Tables 5 6 7 Our intralaboratory generated data is expected to achieve similar results Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QC Office REFERENCES EPA 8141B SW 846 Revision 2A 1999 Methods for the Chemical Analysis of Waters and Wastes Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 9 27 04 Revision 4 1 53 8141 Page 16 of 16 TABLE 7 PERCENT RECOVERY OF 27 ORGANOPHOSPHATES BY SOXHLET EXTRACTIO
241. g the plasma before beginning integration of the background corrected signal to accumulate data When possible use the average value of replicate integration periods of the signal to be correlated to the analyte concentration Flush the system for a total of 60 seconds with the rinse blank and then the next sample The calibration line should consist of a minimum of a calibration blank and a high standard Replicates of the blank and highest standard provide an optimal distribution of calibration standards to minimize the confidence band for a Revision 4 1 7 200 7 Page 16 of 21 straight line calibration in a response region with uniform variance 11 4 5 After completion of the initial requirements of this method samples should be analyzed in the same operational manner used in the calibration routine with the rinse blank also being used between all sample solutions LFBs LFMs and check solutions 11 4 6 During the analysis of samples the laboratory must comply with the required quality control described in Sections 9 5 and 9 6 Only for the determination of dissolved analytes or the direct analysis of drinking water with turbidity of 1 NTU is the sample digestion step of the LRB LFB and not required 11 4 7 Any elements with a concentration above the verified linear range must be diluted Also for the interelement spectral interference correction routines to remain valid during sample analysis the interferant conc
242. gestion volumes are entered in LIMS as the initial and final volumes 11 1 2 Dilutions of the digest are entered into the DIL column of LIMS 11 2 If diluted samples read below 0 1 mg L re analyze using more sample and diluting to a final volume of 20mL Ideally diluted samples should fall in the middle or upper part of the calibration curve 11 3 Do not report results higher than the highest calibrator Digestate may be diluted in half with digested digestion reagent If further sample dilution is necessary re digest a smaller aliquot 11 4 Watch for possible carry over Studies have shown that carry over may occur over a concentration of mg L Rerun samples at or above the reporting limit that following a sample at this concentration Be mindful of carry over that may happen in the digestion block 11 5 If a sample produces a negative peak that is more negative than the reporting limit redigest sample at full strength and reanalyze If the result is still negative the sample is spiked at the reporting limit to demonstrate that matrix interference is not masking actual reportable Kjeldahl nitrogen in the sample Recovery of the 0 1 mg L spike should be at 50 150 If recovery is lt 50 dilute sample re spike and rerun If problem persists re digest a smaller aliquot of sample 11 6 Organic Nitrogen mg L Kjeldahl nitrogen mg L Ammonia nitrogen mg L 11 7 Total Nitrogen mg L Kjeldahl nitrogen mg L Nitrate nitrogen
243. han two weeks must have either a foam plug or screw cap 7 1 2 The pH of media is recorded after autoclaving One tube from each batch of media made is autoclaved in a beaker along with the prepared media The tube is allowed to cool to room temperature before the pH is taken If pH is outside the following acceptance criteria new media is prepared 7 1 2 1 Lauryl Sulfate Broth 6 8 0 2 7 1 2 2 Brilliant Green Bile 7 2 0 2 7 1 2 3 EC Media and EC MUG 6 9 0 2 7 1 3 Each batch of media prepared is tested with a positive and negative control 7 1 3 1 When a batch of media is prepared four tubes are designated as QC tubes 7 1 3 2 After being autoclaved one tube is inoculated with Escherichia coli one tube with Enterobacter aerogenes one tube with Pseudomonas aeruginosa and the last tube is designated as a blank 7 1 3 3 These tubes are incubated for 48 hours at 35 0 0 5 Their results are recorded in the Bacteriology QC log book Eosin methylene blue agar 18 8g media for every 500 mLs of Nanopure Final pH must be 7 1 0 2 See ESB SOP sections 5 2 and 5 3 for agar preparation instructions Dilution water bottles See ESB SOP section 5 0 Reagent water Nanopure Our laboratory uses reference cultures of organisms obtained from ATCC American Type Culture Collection The reference cultures are stored at 4 until manufacturers due date Reference cultures are rehydrated in lauryl sulfate broth at 35
244. he amount of analyte in a non spiked sample and S is the amount of spike added Control limits of 85 to 11596 will generally be used for percent recovery Table 2 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 5 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Table 2 Quality control criteria for field and laboratory measurements Accuracy Precision Spike Target PARAMETER RPE RPD Recovery Reporting Limits Field Analyses dissolved oxygen DO NA 596 NA 0 1 mg L water temperature NA 196 NA 0 01 C specific conductance NA 196 NA 0 01 mS cm pH NA 196 NA 0 01 turbidity NA 1596 NA 0 1 NTU water clarity Secchi depth NA 1096 NA 0 05 m oxidation reduction potential NA 1096 NA 1mv LABORATORY ANALYSES ammonia nitrogen NH4 N 15 15 85 115 0 04 mg L nitrate nitrite nitrogen lt 15 lt 15 85 115 0 04 mg L soluble reactive phosphorus SRP lt 15 15 96 85 115 0 04 mg L total suspended solids TSS 20 96 20 96 NA 0 01 mg L biochemical oxygen demand BOD 20 96 20 NA 5 mg L chemical oxygen demand COD 15 96 15 96 85 11596 3 mg L chlorophyll a 15 96 15 96 NA 10 mg L total phosphorus TP 15 96 15 96 85 115 0 1 pg L total dissolved solids TDS lt 15 15 96 85 115 0 02 mg L total hardness lt 15 15 96 NA 50 mg L dissolved organic carbon DOC
245. he pH to 2 If the sample is reactive upon addition of acid the splitter lets the reaction finish and then rechecks the pH A field blank is prepared and analyzed if required by the data user Use the same container and acid as used in sample collection Samples containing turbidity 1 NTU will be determined by direct analysis Screen acidified samples by testing an aliquot in a turbidimeter meter Results are recorded in the logbook Samples containing turbidity gt 1 NTU must be digested prior to analysis If analysis begins 16 hours after sample preservation and pH verification a qualifier will accompany the data 9 0 QUALITY CONTROL Note See also ESB SOP 01 for general QC requirements 9 1 9 2 Edward S Babcock amp Sons operates a formal quality control QC program The requirements of this program consist of an initial demonstration of laboratory capability and the periodic analysis of laboratory reagent blanks fortified blanks LCS s and other laboratory solutions as a continuing check on performance The laboratory maintains performance records that define the quality of the data thus generated Demonstration of Method Capability 9 2 1 The Demonstration of Method Capability is used to characterize instrument performance analysis of quality control samples and laboratory performance determination of method detection limits prior to analyses of this method conducted by this laboratory 9 2 2 Linear dynam
246. hemical analysis 5 2 Seealso SOP S02 Compressed Gas Cylinder Handling SOP S03 Spill Control Policy Revision 4 1 53 8141 Page 5 of 16 6 0 APPARATUS and EQUIPMENT 6 1 1L amber bottles for sampling aqueous samples Wide mouth jars of various sizes for sampling solids 6 2 Autosampler Vials glass with crimp cap 6 3 Standard laboratory glassware is used See SOP O05 and O51 for extraction glassware 6 4 GAS CHROMATOGRAPH Analytical system complete with temperature programmable GC suitable for use with capillary columns and all required accessories including syringes analytical columns gases detector and data All results are reported from the primary column and confirmed using the secondary column unless analytical conditions and quality control samples indicate that the secondary column results are more accurate See ESB SOP Q20 for details If in any case the secondary column is used for quantification the analyst must document reasoning for doing so 6 4 Column 1 Primary detector NPD 30m long x 0 25mm I D Equity SPB 5 bonded fused silica column 0 25um film thickness Helium carrier gas flow is established at ImL min linear velocity The injection volume is 2uL splitless pulsed injection with purge flow to split vent at 30mL min for 0 75 minutes Initial pulse is 45psi for 0 5min The injector temperature must be 250 C and the detector temperature 330 C GC Conditions Initial temp 40 Hold1 0 min
247. hese results will be used Otherwise data will be rejected and flagged accordingly B6 INSTRUMENT EQUIPMENT TESTING INSPECTION AND MAINTENANCE REQUIREMENTS laboratories contracted by the TASK FORCE and or SJRIPP will operate using quality assurance and quality control programs to maintain their equipment in accordance with their SOPs which include those specified by the manufacturer and those specified by the method Laboratories are required to submit a copy of their SOPs for laboratory equipment maintenance to the TASK FORCE Quality Assurance Manager for review and approval Please refer to the report Appendices A amp B for available laboratory SOPs B7 INSTRUMENT CALIBRATION AND FREQUENCY laboratories contracted by the TASK FORCE and or SJRIPP will operate using quality assurance and quality control programs to calibrate their equipment in accordance with their SOPs which include those specified by the manufacturer and those specified by the method Laboratories are required to submit a copy of their SOPs for laboratory equipment calibration to the TASK FORCE Quality Assurance Manager for review and approval Please refer to the report Appendices amp B for available laboratory SOPs field instruments for each component of the San Jacinto QAPP will be inspected and calibrated prior to visiting the field equipment used to provide numerical data will be calibrated to the accuracy requirements for its use prior to an
248. ibration curve Equation 2 C ug L KASAS A is RF Vo where A s Response for the parameter to be measured A is Response for the internal standard I s Amount of internal standard added to each extract ug Vo Volume of water extracted L 13 3 LIMS Calculation 13 3 1 Aqueous samples 1L of sample is concentrated down to 5mL 13 3 1 1 13 3 1 2 13 3 1 3 13 3 2 Solid samples 13 3 2 1 13 3 2 2 13 3 2 3 LIMS Initial volume 1000 mL units ug L LIMS Final volume 5 mL units ug L Run Data multiplier 5 misc 200 units ug L Data in the run is calculated with calibration standards at the ppm level however results are displayed as ppb This 1000 times factor plus a multiplier of 5 takes into account the prep concentration so that results in the run are displayed as final results When data is transferred to LIMS the misc field converts results back to raw results so that LIMS can apply the initial and final concentration value Since the miscellaneous field also affects RL s and MDL s the analyst must manually adjust these limits back in LIMS by dividing the limits by 200 15g of sample is concentrated down to 5mL LIMS Initial volume 15g units mg L LIMS Final volume 5mL units mg kg Run Data multiplier 0 333 misc 3 units mg kg 13 3 3 Sludge samples 5g of sample is concentrated down to 5mL 13 3 3 1 13 3 3 2 13 3 3 3 LIMS Initial volume 5g units mg L LIMS Final volume 5mL units m
249. ic Revision 5 0 Page 4 of 9 O26 TOC flask The instrument provides automated dilution for the other concentrations The 0 3mg L standard is made by diluting 2mL of a 3mg L standard up to 20mL with TOC reagent water The Make standards before each run and place them in 40ml vials Place standards in the autosampler rack in positions according to the prep sheet The 4mg L and 20mg L standards are also the continuing calibration check sources These are prepared by adding the 2000ppm intermediate standard into 20ml TOC reagent water in the following amounts 40ul and 200ul 8 4 LCS ICV Standards 8 4 1 8 4 2 8 4 3 8 4 4 LCS Stock Second source of Potassium Acid Phthalate purchased from a certified vendor and kept for 10 years LCS Intermediate Add 425mg of dried Potassium Acid Phthalate to 100ml of TOC reagent water This will be equivalent to 2000mg L of organic carbon This solution is stored at room temperature for up to a year LCS Working 4mg L Add 40ul of the LCS Intermediate to 20ml of TOC reagent water Make fresh daily Place in a 40ml VOA vial ICV Working 20mg L Add 200ul of the LCS Intermediate to 20ml of TOC reagent water Make fresh daily 8 5 Solid Standards 8 5 1 8 5 2 Glucose 40 carbon at 99 5 purity 39 79 carbon purchased from a certified vendor This salt is stored at room temperature for up to 10 years 8 5 1 1 A calibration curve is made by analyzing 2 5mg 10mg 20mg 3
250. ic bottles or snap caps in the refrigerator on the sulfuric preserved cart Revision 5 0 I07 COD Page 2 of 7 Draft 4 0 Interferences 4 Chlorides Chlorides are quantitatively oxidized by dichromate and represent a positive interference Mercuric sulfate is added to the digestion tubes in the Hach reagent to complex the chlorides This is effective for chloride levels of 2000mg L or less High concentrations of chloride will precipitate and become turbid when added to the COD solution Samples with higher amounts of chloride are diluted until the chloride level is no longer an interferent 4 2 Discard vials that are scratched or blemished 5 0 Safety 5 Safety goggles and gloves are recommended during this procedure since the reagent vials contain sulfuric acid which will heat up when the sample is added as well as other hazardous chemicals such as dichromate and mercury 5 2 See SOP S01 Concentrated Acids and Bases SOP S03 Spill Control Policy 6 0 Apparatus 6 1 Biospec Tissue Tearer 6 2 Drying oven or block digestor 150 C 6 3 HACH Digestion vials with digestion solution for COD 0 1500ppm 6 4 Spectrophotometer Genesys 10uv 6 5 Standard laboratory glassware volumetric flasks beakers graduated cylinders pipettes Note glassware is cleaned immediately prior to and after use by thorough rinsing with three portions of D I water If glassware still appears dirty further steps are taken by use of one o
251. ic range LDR The upper limit of the linear dynamic range must be established The LDR should be determined by analyzing succeedingly higher standard concentrations of the analyte until the observed value is no more than 10 below the stated concentration of the standard Analyte concentrations above 90 of the determined upper range are diluted For those analyses that are known interferences and are present at above the linear range the analyst ensures that the interelement correction has been applied correctly New dynamic ranges should be determined annually or whenever there is a significant change in instrument response 9 2 3 Quality control sample QCS When beginning the use of this method verify calibration standards and acceptable instrument performance with the preparation and analyses of a QCS The determined mean concentrations from 3 analyses of the QCS must be within 5 of the stated values If the calibration standard cannot be verified performance of the determinative step of the method is unacceptable The source of the problem must be Revision 4 1 Page 10 of 21 9 2 4 M07 200 7 identified and corrected before either proceeding on with the initial determination of method detection limits Method detection limit MDL MDL s are established whenever there is a change in instrumentation or a major modification to the analysis MDL s must be established for all wavelengths utilized using reagent wa
252. ical batch and at a minimum of once for every 20 samples per matrix type This control will be compared to acceptance ranges of 80 120 recovery If the control does not fall within acceptance ranges the analysis is considered to be out of control No further samples shall be analyzed until the out of control condition is corrected Method Blank A sample consisting of 5mL of digestion reagent is digested and analyzed as the method blank One Method Blank will be run with every analytical batch and at a minimum of once for every 20 samples per matrix type It must read below but not more negative than the RL for batch acceptance Samples results reported must be accompanied with a note if the method blank exceeds a concentration greater than 1 10 of the measured raw concentration of the sample however blank results below the RL are considered to be ND and will not require a note Note The blank value noted in the NBLK qualifier is the raw blank result If the sample being qualified was diluted in addition to NBLK the analyst must also attach the qualifier NBLKd which includes the sample raw result 10 4 10 5 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 3 times the estimated IDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit 10 4 1 LOD Verification On a yearly basis a QC
253. icated in the Quality Assurance Manual Percent recoveries are compared to laboratory acceptance ranges If recoveries do not fall within the control limits laboratory personnel must check for errors in the analysis See SOP Q06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager Quality Control Charts are available in LIMS indicating the percent recoveries mean standard deviation UCL and LCL 1 4 Precision Data Matrix Spike Duplicates MSD Sample Duplicates DUP or Laboratory Control Duplicates LCSD 1 4 1 1 4 2 1 4 3 1 4 4 1 4 5 In general precision data is a measurement of the reproducibility of results within the sample matrix Using good laboratory technique duplicate results from a homogeneous sample should agree closely Results from a non homogeneous sample might not agree as well but if a representative sample is taken the results should still be fairly close The larger the sample taken from a non homogeneous matrix the more representative the sample is likely to be Samples for duplication are chosen at random rotated among clients Samples that pose unusual obvious matrix problems however are rejected as an unrepresentative choice for the batch Precision data is obtained from duplicate spikes or from duplicate runs of the sample or Lab Control Duplicate sample runs are used Revision 7 0 Page 5 of 14
254. idered to be ND and will not require a note 9 3 2 Laboratory fortified blank LFB The laboratory analyzes at least one LFB Sect 7 9 with each batch of samples per matrix type or 1 20 whichever is more Calculate accuracy as percent recovery using the following equation Revision 3 0 M12 200 8 Page 13 of 26 where percent recovery LFB laboratory fortified blank s concentration equivalent of analyte added to fortify the LRB solution 9 3 3 Ifthe recovery of any analyte falls outside the required control limits of 85 115 that analyte is judged out of control and the source of the problem is identified and resolved before continuing analyses 9 3 4 The laboratory uses LFB analyses data to assess laboratory performance against the required control limits of 85 115 Sect 9 3 2 When sufficient internal performance data becomes available usually a minimum of twenty to thirty analyses optional control limits can be developed from the mean percent recovery x and the standard deviation S of the mean percent recovery These data can be used to establish the upper and lower control limits as follows UPPER CONTROL LIMIT x 3S LOWER CONTROL LIMIT x 3S 9 3 5 The optional control limits must be equal to or better than the required control limits of 85 115 Also the standard deviation S data should be used to establish an on going precision statement for the level of concentrations included in the
255. iew Review paperwork and data on screen by examining the following 3 6 1 QC recovery and results appear correct in relation to raw results 3 6 2 Batch is acceptable 3 6 3 Hlags are appropriate 3 6 4 Correct units and Reporting Limits are used 3 6 5 Sample ID makes sense with result Data Approval 3 7 If data looks acceptable 3 7 1 Click on top left corner of screen to highlight entire screen Right click Choose Update Status Choose update to Reviewed 3 7 2 If any lines are not acceptable or not reportable highlight line and right click update to Cancelled 3 7 3 Click Done to close 3 8 If something needs to be edited 3 8 1 Under Laboratory Data Entry Review choose batch to edit batch or sample to edit sample Click edit 3 8 2 Columns with blue headers are the only ones that can be edited 3 8 3 Click save to save changes 3 8 4 Click on Done 3 9 If something needs to be redone 3 9 1 Under Laboratory pick Update status then sample proceed to section 3 9 3 3 9 2 Or in Data Review simply proceed to section 3 9 3 3 9 3 Highlight line of analysis and right click choose create re extract 3 9 4 New line is added as Re with status of available 3 9 5 Update statue of original result to pending if necessary 3 10 When approving an invoice that has redos follow the steps in 3 5 except do not mark all analytes 3 10 1 Once the RE is ready for supervisor review compare the results and documen
256. ight the higher the turbidity Readings in NTU s are made in a nephelometer designed according to specifications outlined in Apparatus A standard suspension of Formazin prepared under closely defined conditions is used to calibrate the instrument 2 2Formazin polymer is used as the turbidity reference suspension for water because it is more reproducible than other types of standards previously used for turbidity standards 2 3A commercially available polymer standard is also approved for use for the National Interim Primary Drinking Water Regulations This standard is identified as AMCO AEPA 1 available from Amco Standard International Inc 3 0 Sample Handling and Preservation 3 1Samples may be stored in either plastic or glass Revision 5 0 I36 Turbidity Page 2 of 7 3 2Preservation consists of refrigeration or icing to 4 C to minimize microbiological decomposition of solids 3 3Analysis must be performed within 48 hours per 40CFR section 136 Table Samples must be stored at 4 C 4 0 Interferences 4 1The presence of floating debris and coarse sediments which settle out rapidly will give low readings Finely divided air bubbles will affect the results in a positive manner 4 2 The presence of true color that is the color of 4 3 water which is due to dissolved substances which absorb light will cause turbidities to be low although this effec
257. ile transparency will be determined using a Secchi disk following the sampling methods presented in Table 9 Lake depth and time of sampling at each of the sites will also be noted sampling is expected to be completed before noon under typical conditions Field data will be recorded at the time of sampling in field logs that will be transferred to an Excel spreadsheet in the lab Depth integrated surface 0 2 m whole water column 0 bottom and discrete bottom water samples within approximately 50 cm of the sediments will be collected at each sampling site as shown in Figure 5 Depth integrated samples will be collected using a tube sampler while discrete bottom water samples will be obtained using a van Dorn sampler Water samples will be stored in clean opaque polypropylene bottles on ice and returned to the laboratory Table 9 Samples for dissolved iron Fe analyses will be filtered and acidified in the field using metals grade nitric acid HNO3 A total of eight different bottles are collected for each sample site depth Triplicate samples from each site will be collected three times per year spring summer and fall to quantify sampling variance in measured water quality Canyon Lake Nutrient TMDL Monitoring Program As described above for the Lake Elsinore TMDL Monitoring Program in situ measurements of in lake water quality will be collected at specified depths using a Hydrolab DataSonde 4a or equivalent instrument following samp
258. ill appears dirty further steps are taken such as 1 1 acid rinse Glassware is always finished with a final D I rinse Clean BOD bottles with 1 1 HCL and three rinses of D I water Inspect bottles for residue f a more vigorous cleaning is required a stronger acid and heat may be used Always ensure that all acid is thoroughly removed from the bottle prior to use 10 Reagents and Standards Reagents are stored at room temperature for up to six months Discard if there is any sign of biological growth Standard Glucose Glutamic Acid is made fresh daily and stored in the incubator 10 1 Phosphate buffer solution Dissolve 8 5 g KH2PO 21 75 g KoHPOA 33 4 g Na9HPO4 7H50 and 1 7 g NH4CI in 500 ml Nanopure water and dilute to 1 liter PH should be 7 2 10 2 Magnesium Sulfate solution Dissolve 22 5 g MgSO4 7H50 in Nanopure water and dilute to 1 liter 10 3 Calcium Chloride solution Dissolve 27 5 g CaCl or 36 5 g H2O in Nanopure water and dilute to 1 liter 10 4 Ferric Chloride solution Dissolve 0 25 g FeCl3 6H 0 in Nanopure water and dilute to 1 liter Revision 5 0 I05 BOD Page 3 of 8 10 5 Standard Glucose or Dextrose Glutamic Acid solution Dissolve 0 15 g C6H1 206 and 0 15 g HO9CCH CH 5 CH NH2 CO9H in Nanopure water and dilute to 500 ml Prepare fresh prior to use Plant 3 mL of solution into the BOD 300 mL bottle The working standard solution is made at double strength therefore 3 mL spi
259. ilute 2 5 ml of 1000ppm stock standard into 50 ml of diluant This solution is stored at 4 up to 28 days 7 4 4 Dilute to make the following calibration standards 7 4 4 1 2 0 mg L standard 2 mL of 50ppm Intermediate into 50 mL of diluant 7 4 4 2 The instrument dilutes the 2ppm standard to the following concentrations 0 02 0 05 0 1 0 4 0 8 and 1 6ppm 7 4 4 3 Calibration Blank diluant Note These solutions are stored at 4 for up to two weeks 7 5 ICV and CCV A second stock source of NH4CI is purchased An intermediate standard is prepared as specified in section 7 4 2 and section 7 4 3 Working standards are stored at 4 for up to two weeks Solutions are prepared as follows 7 5 1 1 5 mg L standard 1 5 mL of 50ppm Intermediate into 50 mL of diluant 7 5 2 1 0 mg L standard 1 mL of 50ppm Intermediate into 50 mL of diluant 7 6 calibration blank is analyzed at the beginning of the run every 10 samples and at the end of the run Results must be less than but not more negative than the RL 7 7 standard at the reporting limit is analyzed at the end of the run This is used to validate samples reported as none detected and to evaluate instrument Revision 5 0 153 NH3 Page 6 of 10 7 8 7 9 sensitivity should calibration checks show a low bias This standard should have a signal greater then the method blank An MDL study is completed whenever major equipment or procedural changes are made Standards
260. imes the claimed LOQ A successful analysis is one where the recovery of each analyte is within the established test method acceptance criteria or client data quality objectives for accuracy 5 3 Raising the RL 5 3 1 5 3 2 5 3 3 Inorganics If a sample is diluted for any reason RL is raised to reflect the dilution Organics 53 2 1 If a sample is diluted due to a chromatographic interference that prevents peak integration the RL is raised to reflect the dilution 5 3 2 2 Ifa sample is diluted because it is over calibration range the RL is raised to reflect the dilution 5 3 2 3 If the above does not apply to all target analytes in one sample report other analytes from the original injection with original reporting limits If a raw result is below the RL but rounds up to a reportable value see ESB SOP Q04 for rounding rules then Element will report that result as a hit for that analyte 6 0 Demonstration of Capability DoC The laboratory evaluates the Precision and Bias of a Standard Method for each analyte of concern for each quality system matrix 6 1 Initial Demonstration IDoC 6 1 1 A demonstration of capability must be completed each time there is a change in instrument type personnel or test method A work cell is an exception see section 6 1 5 6 1 1 1 A column of a different phase constitutes a significant change A new demonstration study is required 6 1 1 2 second instrument of the
261. ing Calibration Standards Dilute Intermediate Standard solution to make the following concentrations Std 1 mL into 50ml Std 4 mL into 40mL PCBSA ppm 0 5 PCBSA 50 20 Std 2 mL into 40mL Std 5 g into IL PCBSA Sppm 2 PCBSA 100ppm 0 1 same as the Int Std Std 3 mL into 50mL PCBSA 10 3 9 5 6 Lab Controls The LCS used is from a noncalibration source 9 5 6 1 The standards below for Cl NO3 and SO are made from 1000ppm stock solution into a graduated cylinder and brought up to volume of 100ml with nanopure mL of 1000ppm stock Cl 50 5 50ppm 5 SO 50 5 9 5 62 LCS Standard 25ppm 9 5 6 2 1 Stock Standard Salt 4 Chlorobenzenesulfonic acid purchased from a certified vendor that is from a noncalibration source 9 5 6 2 2 Intermediate Standard 100ppm Weigh 0 1g of Chlorobenzenesulfonic acid into 1L of nanopure 9 5 6 2 3 Working Standard Dilute 10ml of the intermediate standard into 40ml of nanopure Revision 7 0 119 Anions Page 9 of 15 9 5 7 Matrix Spikes Cl SO Add the below aliquots into a 5mL sample Apply a dilution factor of 1 035 to the matrix spike result Aliquot Cl High 50 ppm 25 uL of 10 000ppm stock NO High 20 ppm 100 uL of 1000ppm stock SO High 100 ppm 50 uL of 10 000ppm stock 10 0 Quality Control Note See also ESB SOP 001 for general QC requirements 10 1 Our laboratory has a formal quality control program The minimum req
262. ing time for this test is 28 days We analyze most samples within 24 hours according to EPA 120 1 Revision 5 0 Page 2 of 7 114 7 0 Interferences 8 0 Safety Issues The specific conductance cell can become coated with oil and other materials It is essential that the cell be thoroughly rinsed Platinum electrodes can degrade and cause erratic results The electrode should be inspected periodically If the coating appears to be thin or if it is flaking off the electrode should be re platinized or a new electrode should be purchased General laboratory safety procedures are sufficient for this test See Chemical Hygiene Plan 9 0 Instrumentation Equipment 9 1 Conductivity meter capable of measuring conductivity with an error lt 1 or 1 pmho cm whichever is greater YSI 3100 Conductivity Temperature Instrument 9 2 Platinum electrode YSI Model 3252 9 3 Thermometer 9 4 Water bath with tube rack and tubes Ss Note are taken 4 1 Tubes are cleaned immediately after use by thorough rinsing with three portions of D I water and stored upside down to dry If glassware still appears dirty further steps by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 10 0 Standards 10 1 0 01M KCl Calibratio
263. ining each analyte at 1000 times selected concentration was prepared With a syringe add 1 mL of the concentrate to each of at least four 1 L aliquots of reagent water for aqueous studies and onto sand for nonaqueous studies analyze each aliquot according to procedures beginning in Section 11 Past studies were performed at the following Chlordane less than or equal to the RL Toxaphene at the RL For each analyte the mean recovery value of four of these samples must fall in the proper acceptance range For aqueous samples 70 13096 with a RSD 20 For poorly performing analytes the criteria from Table 12 of EPA Method 8081A is utilized For analytes not found in Table 12 the range is set to equal that of a similar poor performing analyte For nonaqueous samples 70 130 with a RSD 2096 For poorly performing analytes the criteria from Table 9 of EPA Method 80814 is utilized For analytes not found in the table the range is set to equal that of a similar poor performing analyte Since data is compared to performance data developed from single laboratory data certain analytes may be outside the limits however the majority should be within the acceptance limits per 8000B sec 8 4 7 8 4 ASSESSING SURROGATE RECOVERY 8 4 1 When surrogate recovery from a sample or method blank is not within historically generated acceptance limits check calculations to locate possible errors fortifying solutions for degradation contamination o
264. inore amp Canyon Lake Nutrient TMDL QAPP Page 15 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Figure 5 Sampling Sites on Lake Elsinore Laud e 2 Dr Anderson s Station e 4 c Implementation of a Nutrient TMDL monitoring program in Canyon Lake The Canyon Lake nutrient monitoring program will determine compliance with interim and final nitrogen phosphorus chlorophyll a and dissolved oxygen numeric targets In addition the monitoring program will evaluate and determine the relationship between ammonia toxicity and the total nitrogen allocation to ensure that the total nitrogen allocation will prevent ammonia toxicity in Canyon Lake This component of the nutrient TMDL monitoring program includes the measurement of 21 water quality constituents and three additional parameters to be derived from directly measured parameters by calculation as listed in Table 4 At a minimum samples will be collected monthly from October to May and biweekly from June to September at four locations M1 M2 El and E2 within Canyon Lake as shown in Figure 6 Station M3 is an additional station for collection of data for use by UCR students Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Table 4 Canyon Lake Parameters to be Monitored Page 16 water temperature total suspended solids TSS specific conductance chemical oxygen dem
265. ion is verified at the beginning of each run by the analysis of a midpoint calibration check for all single component analytes A low level calibration check for each multi component analyte is also injected see section 7 3 3 Every 10 samples and at the end of the run analysts use 2 different concentration mixtures of single component analytes for calibration verification If multi component analytes are detectable in a sample then a calibration was performed with that run and a calibration check for Toxaphene and or Chlordane is analyzed at the end of the run to bracket results Revision 4 0 Page 10 of 16 7 4 4 7 4 5 7 4 6 7 4 7 54 8081 7 4 3 1 The calibration factor for each single component analyte should not exceed a 15 percent difference from the mean calibration factor calculated for the initial calibration If a non linear calibration model or a linear model not through the origin has been employed for the initial calibration consult Sec 7 of Method 8000 for the specifics of calibration verification CF CF V Difference x 100 7 4 3 2 85 or more of all single component analytes in an individual CCV must fall within the acceptance criteria of 15 All reportable results for target analytes must be qualified if that individual analyte was outside CCV criteria See Q06 for additional details If the results still do not agree a new calibration curve is prepared 7 4 3 3 If the average of
266. ion of Continuing Proficiency On an annual basis analysts must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 2096 Performance Evaluation Studies performed twice a year Definitions See SOP Q15 SOP Definitions Corrective Action For Out of Control Or Unacceptable Data 13 1 See SOP Q06 Corrective Action Pollution Prevention and Waste Management 14 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S07 Pollution Prevention 14 2 Waste Disposal Each sample vial s contents must be poured into a COD only waste receptacle and the empty vials must be discarded only into the GLASS ONLY waste receptacle The COD only waste receptacle is handled by a Waste Disposal company Revision 5 0 I07 COD Page 7 of 7 Draft 15 0 Method Performance Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QA Office References EPA 410 4 Methods for the Chemical Analysis of Waters and Wastes Standard Methods For the Examination of Water and Wastewater APHA AWWA WPCF 18 Edition 5220 D Note All italicized items are an indication of a variation from the method Approved by Date Revision 5 0 I14 EC Page 1 of 7 ELE
267. is performed and all samples are rerun starting from the last acceptable LCS 10 6 Matrix Spike and Matrix Spike Duplicate 10 6 1 10 6 2 Matrix spikes are performed at a frequency of 10 by analysis of a MS every 10 samples per matrix type MSD is done per 20 samples Historical limits are used for percent recovery requirements with a maximum RPD of 20 If the concentration of fortification is less than 25 of the background concentration of the sample the matrix recovery should not be calculated and a qualifier QM4x is attached 10 7 Replicates are analyzed for solid samples The maximum allowable RPD is 40 10 8 When doubt exists over the identification of a peak in the chromatogram confirmatory techniques such as sample dilution and fortification must be used Revision 7 0 119 Anions Page 11 of 15 10 9 Linear Calibration Range This method uses an eight point calibration curve so that if any portion of the range is shown to be nonlinear that portion is clearly defined Results are not accepted over the high standard value 10 10 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 3 times the estimated MDL A minimum of seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit The MDL of the least sensitive instrument is entered into LIMS 10 10 1 LOD Verification On a yearly basis an
268. ish instrument software run procedures for quantitative analysis For all sample analyses a minimum of three replicate integrations is required for data acquisition Use the average of the integrations for data reporting 11 4 4 All masses that might affect data quality are monitored during the analytical run As a minimum those masses prescribed in Table 4 are monitored in the same scan as is used for the collection of the data This information 1s used to correct the data for identified interference 11 4 5 During the analysis of samples the laboratory must comply with the required quality control described in Sections 9 3 and 9 4 Only for the determination of dissolved analytes or the direct analysis of drinking water with turbidity of 1 NTU is the sample digestion step of the LRB LFB and LFM not required 11 4 6 The rinse blank is used to flush the system between samples Allow sufficient time to remove traces of the previous sample 35 seconds for wastewaters and ground waters 25 seconds for drinking waters Samples are aspirated for a minimum of 30 sec prior to the collection of data Revision 3 0 M12 200 8 Page 19 of 26 11 4 7 Samples having concentrations higher than the high check standard are diluted into range and reanalyzed The sample is first analyzed for the trace elements in the sample protecting the detector from the high concentration elements if necessary by the selection of appropriate scanning windows
269. ive Date 09 22 06 1 0 and Application 2 0 3 0 4 0 5 0 This method covers the determination of total Kjeldahl nitrogen in drinking and surface waters domestic and industrial wastes This method may also be used for solid samples if both client and regulator agree to this variation 12 Analytically organic nitrogen and ammonia are determined together as Kjeldahl nitrogen Organic nitrogen includes such natural materials as proteins and peptides nucleic acids and urea and numerous synthetic organic materials Typical organic nitrogen concentrations vary from a few hundred ug L in some lakes to more than 20 mg L in raw sewage This procedure converts nitrogen components of biological origin but may not convert all the nitrogenous compounds of some industrial wastes Working Range 0 1mg L to 3 0mg L This range is for photometric measurements made at 660nm in a 10 mm tubular flow cell Higher concentrations can be determined by sample dilution Summary The sample is heated in a block digester in the presence of sulfuric acid potassium sulfate and mercuric sulfate The residue is cooled and diluted with Nanopure water The ammonium ion is determined using an automated colorimetric analyzer Collection Preservation and Holding Time 41 Samples are preserved to pH 2 with sulfuric acid They are stored at 4 degrees Celsius 4 2 Samples must be analyzed within 28 days Interferences 5 1 The acid and salt co
270. ive cleanup of solvents reagents and glassware may be required to eliminate background phthalate ester contamination Glassware must be scrupulously cleaned Clean all glassware as soon as possible after use by rinsing with the last solvent used This should be followed by detergent washing with hot water and rinses with tap water and organic free reagent water Drain the glassware and dry it or rinse with the appropriate solvent hexane for solids methylene chloride for liquids Store dry glassware in a clean environment The presence of elemental sulfur will result in broad peaks that interfere with the detection of early eluting organochlorine pesticides Sulfur contamination should be expected with sediment samples Method 3660 is suggested for removal of sulfur Since the recovery of Endrin aldehyde using the TBA procedure is drastically reduced this compound must be determined prior to sulfur cleanup Waxes lipids and other high molecular weight materials can be removed by Method 3640 gel permeation cleanup Other halogenated pesticides or industrial chemicals may interfere with the analysis of pesticides Certain co eluting organophosphorus pesticides are eliminated by Method 3640 gel permeation cleanup pesticide option Co eluting chlorophenols may be eliminated by using Method 3630 silica gel Method 3620 Florisil or Method 3610 alumina Polychlorinated biphenyls PCBs also may interfere with the analysis of the organoch
271. k Perform Winkler titration on the same bottle as per above procedure 11 1 1 through 11 1 9 10 2 2 1 4 Probe Blank Set up another bottle to incubate Perform a DO reading by probe and then by Winkler 10 2 2 2 Standard 10 2 2 2 1 Winkler Standard Set up a standard check by adding 3 ml of the Standard Glucose Glutamic Acid solution BOD SOP I05 section 10 5 into the 300 ml BOD bottle 10 2 2 2 2 Take a probe reading 10 2 2 2 3 DOo Probe reading and Winkler reading 10 2 2 3 If the probe result varies more than 0 4 from the Winkler titration try the titration again If result still varies perform proper maintenance and repeat probe reading 10 2 2 4 When evaluating results consider several factors to determine if probe is performing correctly membrane appearance Winkler standard Winkler blank LCS and MB results 10 2 3 Samples are read by taking the LED readout when a stable reading has been reached It is important that no air bubbles are trapped in between the neck of the bottle and the probe Make sure to rinse probe between sample readings Revision 4 0 124 DO Page 5 of 6 10 2 4 After reading the sample the probe should be carefully removed from the bottle with a gentle twisting motion and rinsed to remove any excess sample The probe is ready for the next sample 10 2 5 Clean BOD bottles with 1 1 HCL and three rinses of D I water Inspect bottles for residue f a more vigorous cleani
272. k standards and Winkler standards 11 2 3 Determine dilution amount by past experience or odor of sample Check with lab director Clean samples require a 40 dilution f the dilution is greater than 0 1 ml in 300 ml than a serial dilution is needed 11 2 4 Using wide tip pipette or graduated cylinder deliver desired amount of sample to each bottle by predetermined dilutions Sample has been stored at 4 and may or may not be 20 upon dilution 11 2 5 The dilution of the lab control is set to result in 200 ppm This is achieved by adding 3 ml of the Standard Glucose Glutamic Acid solution into the 300 ml BOD bottle 11 2 6 Fill each bottle with prepared water preventing any air bubbles in the bottles Form a water seal by allowing water to fill flare top to the lip of the bottle to ensure no air will be trapped under stoppers after D O reading 11 2 7 Determine the initial dissolved Oxygen see Dissolved Oxygen procedure SOP 124 of samples using DO bottles 11 2 7 1 Ifthe DO is considerably lower 1 mg L than the other DO s and blanks then redo that sample with a lesser volume 11 2 7 2 If the DO is considerably higher more than 9 mg L reduce DO to saturation by bringing another portion of sample to about 20 degrees Centigrade in a partially filled BOD bottle while agitating by vigorous shaking or by aerating 11 2 8 Before placing ground glass stoppers into bottles add more water to top of bottle if necessary Cover ea
273. ked into a BOD bottle represents a 2 dilution 10 6 Sulfuric Acid Solution Add 5 drops concentrated sulfuric acid to 100 mL of Nanopure Water 10 7 0 25N NaOH Solution Add 1 gram of NaOH to 100 mL of Nanopure Water 10 8 Sodium Sulfite Titrant Dissolve 0 7895g of Na2SO3 into 500 mL of Nanopure water Prepare fresh daily 10 9 Orthotolidine Solution Dissolve 1 35g orthotolidine dihydrochloride into 500 mL Nanopure water Prepare separately a solution of 150 mL HCI and 350 mL Nanopure water always add acid to water Combine the two solutions 10 10 Nitrification Inhibitor contains 2 chloro 6 trichloro methyl pyridine TCMP 10 11 Reagent water Nanopure or D I Water 11 Procedure 11 1 Sample Pretreatment 11 1 1 Test to determine if residual chlorine is present in the sample 11 1 1 1 Pre screen for chlorine with ortho tolidine solution Add one or two drops of ortho tolidine solution to 5 ml of sample Yellow color chlorine present 11 1 1 2 Place 200 ml of sample into a flask Add 0 5 mL Sulfuric Acid few crystals of Potassium Iodide and a few drops of starch solution see Dissolved Oxygen SOP 124 Titrate using Sodium sulfite solution until blue color disappears Determine the amount of Thiosulfate titrant needed to destroy the residual Chlorine in the amount of sample used for dilution 11 1 1 3 Calculation Amount of Sodium sulfite solution from 11 1 1 2 x Amount of sample needed for BOD divided by
274. king calibration check An earlier ICV and CCB reprocessed under the new calibration must work to accept the calibration All data must be bracketed by working QC The decision to accept any data when a IPC is out must be clearly documented and made by the QA Officer Quality Control Sample QCS The QCS is a solution of metals from a noncalibration source After the preparation of new calibration standards analyze three QCS standards Tabulate the mean concentration of the three QCS analyses It must be within 596 of the true value to verify the new standards Initial Calibration Verification ICV The ICV is a solution of metals from a noncalibration source The ICV is analyzed immediately following initial calibration Apply the following acceptance criteria 9 5 7 1 The ICV is used to verify initial calibration acceptance criteria 1096 recovery 9 5 7 2 If data must be reprocessed under a new calibration due to instrument drift later in the run a later CCV may be used as the calibrator The ICV must be processed under the new calibration to verify it acceptance criteria 1096 recover Spectral interference check SIC solution The laboratory verifies the interelement spectral interference correction routine by Revision 4 1 Page 13 of 21 M07 200 7 analyzing a SIC solution and blank with each run that contains analytes of interest needing correction It is analyzed at the beginning after every 20 samples and at the end of
275. l 1897 45 6 DCPA 1861 32 1 Dichlone 117 80 6 Dicofol 115 32 2 Etridiazole 2593 15 9 Halowax 1000 58718 66 4 Halowax 1001 58718 67 5 Halowax 1013 12616 35 2 Halowax 1014 12616 36 3 Halowax 1051 2234 13 1 Halowax 1099 39450 05 0 Mirex 2385 85 5 Nitrofen 1836 75 5 Revision 4 0 O54 8081 Page 3 of 16 PCNB 82 68 8 Permethrin cis 4 trans 52645 53 1 Perthane 72 56 0 Propachlor 1918 16 7 Strobane 8001 50 1 trans Nonachlor 39765 80 5 Trifluralin 1582 09 8 2 0 SUMMARY OF METHOD 2 1 2 2 2 3 24 2 5 A measured volume or weight of sample approximately 1 L for liquids 5g for sludge or 15g for solids is extracted using the appropriate matrix specific sample extraction technique Liquid samples are extracted at neutral pH with methylene chloride using Method 3510 separatory funnel to a final volume of 10mL Solid samples are extracted with hexane acetone 1 1 using Method 3550 ultrasonic extraction to a final volume of 5 mL A variety of cleanup steps may be applied to the extract depending on the nature of the matrix interferences and the target analytes Florisil cleanups are performed on samples that appear dirty or have historically required one After cleanup the extract is analyzed by injecting a 2 uL sample into a gas chromatograph with a narrow or wide bore fused silica capillary column and electron capture detector GC ECD 3 0 INTERFERENCES 3 1 3 2 Sou
276. l be evaluated by assessing whether the sampling procedures defined in the SOPs were followed during sample collection The analytical results from replicate samples will also be used to evaluate the representativeness of the field sampling procedures Laboratory Data Laboratory data will be evaluated for representativeness by assessing whether the laboratory followed the specific analytical criteria defined in the SOPs assessing compliance with holding time criteria and the results of method and instrument blank samples and field replicate samples The criteria for laboratory and field blanks will be less than the method detection limit for the target analyte Please refer to the report Appendix A E S Babcock and Sons Inc Laboratory Standard Operation Procedures and Appendix B University of California Riverside Dr Michael Anderson Laboratory Standard Operation Procedures for available laboratory SOPs referred to collectively as Appendices A amp B throughout the document and E S Babcock and Sons Inc Analytical Information Documents Appendix C Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 21 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A8 SPECIALIZED TRAINING REQUIREMENTS Training for all persons involved in the field sampling activities will be conducted prior to any field sampling All individuals that participate in sampling activities are required to have attended at a minimum the 4 hour Basic Site S
277. l monitoring required to support the SJR Component will also be consistent with the TASK FORCE PROGRAMS QAPP procedures Laboratory Analysis The TASK FORCE will contract out all laboratory and field work associated with the implementation of the TASK FORCE PROGRAMS commercial laboratories contracted by the TASK FORCE are required to follow Surface Water Ambient Monitoring Program SWAMP protocols or approved and documented alternative protocols for all proposed laboratory analyses and provide training to its staff as part of its standard operating procedures SOP All laboratories contracted by the TASK FORCE are required to submit a copy of their SOPs for laboratory analyses and quality assurance to the TASK FORCE Monitoring Program Manager and appropriate Quality Assurance Manager for review and approval In addition all laboratories contracted by the TASK FORCE will act as a technical resource to TASK FORCE staff and management Preparation of the OAPP The Quality Assurance Managers will establish and implement the quality assurance and quality control procedures found in this QAPP as part of the sampling and field analysis procedures They will also work with the each of the Quality Assurance Managers by communicating all quality assurance and quality control issues contained in this QAPP The Quality Assurance Managers will also review and assess all procedures during the life of the contract against QAPP requirements The Quali
278. le 9 0 Extra Quality Control Samples 9 1 When the analyst performs QC samples at a frequency that exceeds SOP requirements which are based on method NELAP and ESB laboratory criteria the extra QC may be treated in the following manner 9 1 1 All QC is reported however it must be accompanied with the proper QC qualifier if it is out of laboratory acceptance criteria 9 1 2 Data associated with out of control QC that is considered to be extra does not require a sample qualifier 10 0 Qualifier Note 10 1 If a LCS or MB qualifier is necessary it must be placed on samples associated with the corresponding preparation batch ICV and CCV qualifiers must be placed on samples associated with the corresponding analytical batch or run MS duplicate surrogate or internal standard qualifiers are placed on the sample in question only 10 2 Definitions 10 2 1 Batch environmental samples that are prepared and or analyzed together with the same process and personnel using the same lot s of reagents 10 2 2 A preparation batch is composed of one to twenty environmental samples of the same NELAP defined matrix meeting the above mentioned criteria and with a maximum time between the start of processing of the first and last sample in the batch to be 24 hours 10 2 3 Ananalytical batch or run is composed of prepared environmental samples extracts digestates or concentrates which Revision 7 0 Q06 Page 11 of 11 are analyzed tog
279. le 9 3 Procedure for Neutralizing Acid Samples 9 3 1 500 ul of sample is added to a 50 ml blue tube and brought up to 30 mL with nanopure Then with 6N NaOH the pH is adjusted to between 2 and 3 Finally the sample is diluted up to 50 mL with nanopure for a total dilution of 100 9 3 2 MB and LCS are also prepared in a blue tube 500 ul of 2 H28O4 is added to 30 mL of nanopure The pH is adjusted with 6N NaOH if needed to between 2 and 3 Finally the sample is brought up to 50 mL with nanopure 100ul of Intermediate Standard is added to the LCS tube to make a 4 ppm LCS 9 3 3 AMS and MSD are analyzed with this method 9 4 Calibration 9 4 1 Calibration is performed when CCVs are out of acceptance criteria 9 4 2 Although a 3 point curve plus zero is required a 7 point curve is prepared by plotting instrument response against standard concentration The curve also includes zero 9 4 3 To calibrate the instrument make sure that the temperature of the furnace has equilibrated 9 4 4 Load the file and place the blank standards and ICV in the appropriate positions 9 4 5 Press start Revision 5 0 Page 7 of 9 9 4 6 9 4 7 9 4 8 O26 TOC An acceptable curve yields an r 0 99 or better Calibration Checks 9 4 7 1 ICV Following calibration the 20ppm ICV made from the LCS source is analyzed Results must be within 90 110 of the true value 9 4 7 2 CCV Every 15 samples and at the end of the run a 4ppm or 20p
280. lenium 82 krypton have isobaric elemental interferences If alternative analytical isotopes having higher natural abundance are selected in order to achieve greater sensitivity an isobaric interference may occur All data obtained under such conditions must be corrected by measuring the signal from another isotope of the interfering element and subtracting the appropriate signal ratio from the isotope of interest A record of this correction process should be included with the report of the data It should be noted that such corrections will only be as accurate as the accuracy of the isotope ratio used in the elemental equation for data calculations Relevant isotope ratios should be established prior to the application of any corrections 4 2 Abundance sensitivity Is a property defining the degree to which the wings of a mass peak contribute to adjacent masses The abundance sensitivity is affected by ion energy and quadrupole operating pressure Wing overlap interferences may result when small ion peak is being measured adjacent to a large one The potential for these interferences should be recognized and the spectrometer resolution adjusted to minimize them 4 3 Isobaric polyatomic ion interferences Are caused by ions consisting of more than one atom which have the same nominal mass to charge ratio as the isotope of interest and which cannot be resolved by the mass spectrometer in use These ions are commonly formed in the plasma o
281. les in paragraph 11 2 The final report indicates that the results are for dissolved analytes 11 2 Preparation for direct analysis of total recoverable analytes in samples containing turbidity lt 1 NTU Place in autosampler tube 11 2 1 11 2 2 11 2 3 11 2 4 5 mL of sample 0 5 mL conc HNO 250 uL 50uL of 2000ppm La Internal Standard 11 3 Total Recoverable Analytes See SOP M02 for sample preparation 11 4 Sample Analysis 11 4 1 11 4 2 11 4 3 11 4 4 When a problem is suspected inspect the sample introduction system including the nebulizer torch injector tube and uptake tubing for salt deposits dirt and debris that would restrict solution flow and affect instrument performance Clean the system when needed or on a daily basis Configure the instrument system per manufacturer s instructions The instrument must be allowed to become thermally stable before calibration and analyses This usually requires at least 30 to 60 minutes of operation After instrument warm up complete any required optical profiling or alignment particular to the instrument For initial and daily operation calibrate the instrument according to the instrument manufacturer s recommended procedures using mixed calibration standard solution and the calibration blank A peristaltic pump is used to introduce all solutions to the nebulizer To allow equilibrium to be reached in the plasma aspirate all solutions for 30 sec after reachin
282. level of TDS is essential to the health of aquatic organisms as the density of the TDS determines water flow in and out of cells Elevated TDS levels are not generally health hazards for humans but have an effect on the smell and taste of drinking water 1 3 2The EPA classified TDS as a Secondary Drinking Water Standard and has set a limit of TDS less than 500 mg L for drinking water High concentrations of TDS due to carbonates can lead to scale formation and a bitter taste to the water If a water source tastes salty and an increase in corrosivity is observed it may have a high TDS concentration due to chlorides These effects are not necessarily dangerous but are unpleasant Scale formation is a nuisance as it can be damaging to water heaters and plumbing 2 0 Working Range 10 mg L to 2000 mg L 3 0 Summary of Method Revision 5 0 129 2 8 well mixed aliquot of the sample is filtered through a standard glass fiber filter The filtrate is evaporated and dried at 180 C Revision 5 0 I29 TDS Page 3 of 8 4 0 Definitions See SOP Q15 SOP Definitions 5 0 Sample Handling Sample may be stored at 4 C for up to 7 days as specified in 40 CFR part 136 table gt 6 0 Interferences 6 1 Highly mineralized waters containing significant concentrations of calcium magnesium chloride and or sulfate may be hy
283. libration after every tenth sample and at the end of the sample run Analytes must be lt 12 the reporting limit If one half the reporting limit is less than the MDL calibration blank values must be the MDL for those analytes Instrument performance check Continuing calibration verification IPC CCV solution The IPC CCV is a solution of metals from the same source as the calibration The laboratory analyzes the IPC solution following daily calibration after every tenth sample and at the end of the sample run Analysis of the IPC solution immediately following calibration must verify that the instrument is within 596 of calibration with a relative standard deviation 396 from 3 replicate integrations Subsequent analyses of the IPC solution must be within 10 of calibration If the calibration cannot be verified within the specified limits reanalyze either or both the IPC solution and the calibration blank If the second analysis of the IPC solution or the calibration blank confirms calibration to be outside the limits sample analysis must be discontinued the cause determined corrected and or the instrument recalibrated All samples following the last acceptable IPC solution must be reanalyzed The analysis data of the calibration blank and IPC solution must be kept on file with the sample analyses data Alternately data may be reprocessed using the most recent CCB as the calibrator Reprocess all samples back thru the last wor
284. ling and analytical methods presented in Tables 9 Water samples will be collected as depth integrated samples down to the sediments East Bay or the bottom of the epilimnion when stratified using a tube sampler discrete samples will be collected at the thermocline and at the upper middle and lower regions of the hypolimnion at the three main lake sites as shown in Figure 6 using a van Dorn sampler Hypolimnetic samples will be then composited to yield a depth averaged hypolimnetic sample for each of these sites SJR Component The sampling methods required by the SJR Component Program is the same as described above for the Canyon Lake Nutrient TMDL monitoring program SJRIPP The sampling methods required by the SJRIPP are described in Section A6 of this QAPP Corrective Action Measures Babcock s QA Manual please see Appendix E describes actions that will be undertaken should their laboratory equipment malfunction For field meters extra batteries will be kept in stock Typically a spare pH and TDS meter are kept in stock for quick replacement Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 26 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Table 8 San Jacinto Watershed and SJRIPP Sampling Methods Analysis Recommended ARE Na Parameter SOP Sample Containers Ini
285. ll Control Policy 7 0 Apparatus 7 1 Standard laboratory glassware volumetric flasks beakers tall 200mL capacity graduated cylinders pipettes Note Prior to use glassware is acid rinsed with 1 1 HCI and three rinses of D I All glassware is cleaned immediately after use by thorough rinsing with three portions of D I water If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 7 2 Block Digester SEAL BD 46 7 3 SEAL Discrete Automated Colorimetry 7 4 Vortex 7 5 Hengar Granules 8 0 Standards and Reagents 8 1 Reagent water Prepare all intermediate standards and reagents including dilutions in ammonium free D I water Revision 5 0 Page 3 of 10 I45 KJN 8 2 Laboratory Control Sample LCS 8 2 1 8 2 2 8 2 3 Stock LCS 100 mg L Stock TKN Standard purchased from ERA Solution is stored at room temperature Manufacturer expiration dates are observed Once a stock standard is opened the expiration date is one year as long as this date does not exceed the original manufacturer s date Stock standards can be replaced sooner if comparison with QC samples indicate a problem LCS Digest 0 2mL Stock LCS Dilute to 20mL with Nanopure water after digestion for a final concentration of 1 mg L Acceptability If the LCS doesn t fall within the
286. lorine pesticides The problem may be most severe for the analysis of multicomponent analytes such as Chlordane Toxaphene and Strobane If PCBs are known or expected to occur in samples the analyst should consult Methods 3620 and 3630 for techniques that may be used to separate the pesticides from the PCBs The following compounds may coelute using the dual column analysis scheme In general the HP 5 column resolves fewer compounds that the HP 1701 ZB 1701 Permethrin Heptachlor epoxide Endosulfan I alpha Chlordane Perthane Endrin Endosulfan II Chloropropylate Chlorobenzilate 4 4 DDT Endosulfan sulfate Methoxychlor Dicofol SPB 608 Chlorothalonil beta BHC delta BHC DCPA Permethrin alpha Chlordane trans Nonachlor Nitrofen Dichlone Carbophenothion Dichloran exhibit extensive peak tailing on both columns Simazine and Atrazine give poor responses on the ECD detector Triazine compounds should be analyzed using Method 8141 NPD option Revision 4 0 O54 8081 Page 5 of 16 4 0 APPARATUS AND MATERIALS 41 Gas chromatograph An analytical system complete with gas chromatograph suitable for on column and split splitless injection and all required accessories including autosampler analytical columns gases electron capture detectors ECD and data system 4 1 1 Primary Gas Chromatograph HP 5890 or HP 6890 4 2 Detector Electron Capture Detector 4 1 3 Turbochrome Data Capture 4 4 Primary column ZB 1701 30 m X 0 25 mm
287. lorophyll a 10200 H 3 0 1 ug L 0 1 1000 ug L Standards total phosphorus TP 4500 P 0 02 mg L 0 2 2 mg L Standards total dissolved solids TDS 2540 50 mg L 50 10 000 mg L total hardness 2340 B 0 1 mg L 0 1 300 mg L Standards dissolved organic carbon DOC 5310 C 5 mg L 5 100 mg L Standards total organic carbon TOC 5310 C 5 mg L 5 100 mg L Standards dissolved manganese Mngiss 3120 0 007 mg L 0 007 50 mg L Standards dissolved iron Fegiss 3120 0 004 mug L 0 004 100 mg L Standards total iron Fea 3120 B 0 004 mug L 0 004 100 mg L Standards values for pH and ORP are the minimum difference in readings that can be quantified Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 4 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE 2 Training Graduate students and advanced undergraduate students will generally conduct the field sampling and laboratory analyses New students will be trained by those who have significant prior experience with the specific sampling and analytical protocols to be used When new sampling or analytical methods are used the Quality Assurance manager Anderson will oversee new method setup and implementation and confirm overall method efficacy 3 Quality Control Quality control will be ascertained using replicate analyses reference standards and spike recoveries Analytical precision will be evaluated by analysis of replicate samples Duplicates will be analyze
288. lt 25 percent will be used for relative difference Bias and Accuracy Bias refers to the systematic or persistent distortion of a measurement process that causes errors in one direction above or below the true value or mean The bias of a measurement system is affected by the sample matrix or by errors introduced during sample collection preservation handling preparation and analysis Accuracy is the degree of agreement of a measurement with an accepted reference or true value Accuracy includes a combination of random error and systematic error bias components that result from sampling and analytical operations Field Bias Although bias of the field program cannot be assessed quantitatively a qualitative bias assessment for the study will be conducted by reviewing the sample collection preservation and handling procedures Laboratory Bias Accuracy of analytical data will be evaluated by analyzing reference materials and spiked samples Reference materials will be run with each batch of samples during laboratory analyses Confidence intervals supplied with reference samples will be used as control limits at the 95 percent confidence level The relative percent error RPE of standards will be calculated as follows RPE C Co Co 100 Where C is the concentration analyzed in the sample and Co is the true concentration Spiked samples one per 20 samples or one per batch whichever is more frequent will be used to assess the
289. ltation and unknown toxicity in Lake Elsinore and high bacteria in Canyon Lake As required by the Clean Water Act Section 303 d waters that do not or are not expected to meet water quality standards i e beneficial uses water quality objectives must implement a total maximum daily load TMDL As a result the Regional Board initiated the development of TMDLs for nutrients for Lake Elsinore and Canyon Lake Since 2000 local stakeholders in cooperation with the Regional Board have been working to identify the sources of nutrients causing impairment and evaluate their impacts to water quality and beneficial uses Stakeholders have actively participated in annual watershed wide stormwater quality and flow monitoring as well as water quality monitoring of Lake Elsinore and Canyon Lake Grant funding has enabled stakeholders to develop models of the lakes to better understand the lake characteristics as well as a San Jacinto River Watershed model to simulate the wash off and transport of nutrients to the lakes In addition LESJWA has performed numerous studies of the lakes and started the implementation of projects to bring about improvements to in lake water quality Lake Elsinore and Canyon Lake Nutrient TMDL Program In 2004 the Regional Board prepared the Lake Elsinore and Canyon Lake Nutrient TMDL Report This report framed the stakeholders monitoring and modeling efforts to characterize in lake water quality and thus provided the b
290. ly oxidized to its phosphorotrithioate Merphos oxone Chromatographic analysis of Merphos almost always results two peaks unoxidized Merphos elutes first As the relative amounts of oxidation of the sample and the standard is probably different quantitation based on the sum of both peaks may be most appropriate 4 5 8 Retention times of some analytes particularly Monocrotophos may increase with increasing concentrations in the injector Analysts should check for retention time shifts in highly contaminated samples 4 5 9 Many analytes will degrade on reactive sites in the chromatographic system Analysts must ensure that injectors and splitters are free from contamination and are silanized Columns should be installed and maintained properly 4 5 10 Performance of chromatographic systems will degrade with time Column resolution analyte breakdown and baselines may be improved by column washing Oxidation of columns is not reversible 4 6 NP Detector interferences Triazine herbicides such as Atrazine and Simazine and other nitrogen containing compounds may interfere 5 0 SAFETY 5 1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined however each chemical compound must be treated as a potential health hazard Accordingly exposure to these chemicals must be reduced to the lowest possible level A reference file of material safety data sheets is available to all personnel involved in the c
291. m Also add 20uL of 250ppm surrogate standard and 8uL of 500ppm internal standard 80 SAMPLE COLLECTION PRESERVATION and STORAGE 8 1 8 2 Grab samples must be collected in glass containers Conventional sampling practices should be followed however the bottle must not be pre rinsed with sample before collection Sample Preservation and Storage If residual chlorine is present in aqueous samples add 80mg of sodium thiosulfate per liter of sample to the sample bottle prior to collecting the sample After the sample is collected in a bottle containing preservative s seal the bottle and shake vigorously for 1 min 8 2 1 8 2 2 Revision 4 1 53 8141 Page 9 of 16 8 2 3 The samples must be iced or refrigerated at 4 C away from light from the time of collection until extraction Samples must be extracted within 7 days when stored under these conditions 8 2 4 Immediately prior to extraction aqueous samples are adjusted to a pH of 7 by adding 50mL of Phosphate buffer 8 3 Extract Storage Extracts should be stored at 4 C away from light A 40 day maximum extract storage time is recommended 9 0 CALIBRATION 9 A 5 7 point calibration is used Prepare standards according to recipes in section 7 4 3 9 2 Tabulate response peak height or area against concentration for each compound and internal standard Calculate the response factor RF for each analyte and surrogate using Equation 1 Equation 1 As Ci
292. m Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 10 2 1 5 When this method is used to analyze unfamiliar samples for any of the above anions anion identification should be supported by the use of fortified sample matrix covering the anions of interest if the identity of an analyte is in question 1 6 Environmental Relevance 1 6 1 Nitrate is regulated as a health concern because it has been identified as a cause of methemoglobinemia In freshwater or estuarine systems nitrate can reach high levels that can potentially cause the death of fish Over 30 ppm of nitrate can inhibit growth and impair the immune system of fish 1 6 2 Chloride increases the electrical conductivity of water and increases its corrosivity In metal pipes chloride reacts with metal ions to form soluble salts thus increasing levels of metals in drinking water 1 6 3 Sulfate may have a laxative effect that can lead to dehydration With time the symptoms will disappear as people adapt to the sulfate in the water Sulfate can also cause scale buildup in water pipes and corrode plumbing 1 7 Nitrate Notification If results are 40mg L or above the analyst will notify and hand one of the four Project Managers their results noted on their bench sheets The Project Manager will then notify the client within 24 hours via email or phone call until the client is reached Contact informatio
293. m 89 b Rhodium 103 Indium 115 isobaric interference by Sn Terbium 159 Holmium 165 Lutetium 175 Bismuth 209 a May be present in environmental samples In some instruments Yttrium may form measurable amounts of YO 105 amu and YOH 106 amu If this is the case care should be taken in the use of the cadmium elemental correction equation Internal standards recommended for use with this method are shown in bold face Preparation procedures for these are included in Section 7 5 Revision 3 0 M12 200 8 Page 24 of 26 TABLE 4 RECOMMENDED ANALYTICAL ISOTOPES AND ADDITIONAL MASSES WHICH MUST BE MONITORED Isotope Element of Interest 27 Aluminum 121 123 Antimony 75 Arsenic 135 137 Barium 9 Beryllium 106 108 111 114 Cadmium 52 53 Chromium 59 Cobalt 63 65 Copper 206 207 208 Lead 55 Manganese 95 97 98 Molybdenum 60 62 Nickel 77 82 Selenium 107 109 Silver 203 205 Thallium 232 Thorium 238 Uranium 51 Vanadium 66 67 68 Zinc Krypton Ruthenium Palladium Tin NOTE Isotopes recommended for analytical determination have an next to them Revision 3 0 M12 200 8 Page 25 of 26 TABLE 5 EPA 200 8 RECOMMENDED ELEMENTAL EQUATIONS FOR DATA CALCULATIONS Element Elemental Equation Note Al 1 000 27C Sb 1 000 123C AS 1 000 75C 3 127 77C 0 815 82C 1 Ba 1 000 137C Be 1 000 9C Cd 1 000 111C 1 073
294. me of filtrate A filtered blank must be included with the samples Label blank with date initials along the side of the bottle and list the sample s associated with it Apply the printed label to the samples if it is provided Preserve as specified in section 8 0 placing a SF on the sample bottle and Work Order Printout 3 7 3 For all other analysis Filter sample through a 0 45 micron filter Make sure to filter enough sample for all requested analysis Label the bottle as filtered with date and initials and apply the printed label if it is provided If filtered sample needs to be split out for any other preserved analysis make sure to include a preserved filter blank that is labeled with date initials and sample s associated with it 3 8 notes in comments Place a checkmark next to the note on the Work Order Printout once the directions have been carried out 3 9 All interference screening and preservative addition is noted on the Work Order Printout by a code explained below and in Table 1 3 10 The splitter signs and dates each Work Order Printout after the statement Preservation confirmed by i 4 0 Cyanides CN 4 1 Preserve samples with approximately 1 2 mL of 35 sodium hydroxide per 500 mL of sample to pH gt 12 at the time of collection or as soon as possible at the laboratory Place an OH on the Work Order Printout and sample lid If a sample is received preserved section 4 4 cannot be performed If possible
295. merse electrode several times in and out of solution ensuring that no bubbles are trapped under the electrode and a stable reading is acquired The probe is not placed in successive portions of standard solution as specified in the method however if unusual variations are observed standard solution is re poured and reanalyzed 6 Read the conductance and make sure the reading falls within 90 110 The temperature is also displayed at the bottom of the screen 7 Take the electrode out of the standard rinse it off with D I wash bottle Revision 5 0 Page 4 of 7 Note 1000 11 TI If the conductivity is el displayed in mmhos cm and record your final result in pmho cm 8 Rinse it off with D 114 dry off and place in lab control It must read 90 110 wash bottle dry off and place in a tube of D I water An EC reading of the D I water is read as an internal monitoring of the deionization process 9 Place the clean dry electrode into the first sample Immerse electrode several times in and out of sample ensuring that no bubbles are trapped under the electrode and a stable reading is acquired The probe is not placed in successive portions of sample as specified in the method however if unusual variations are observed samples are re poured and reanalyzed result will be multiply by This must be vated th Record y
296. mg L 8 5 ICV and CCV A second stock source of NH4CI is purchased An intermediate standard is prepared as specified in section 8 4 2 Standards are prepared as follows Revision 5 0 Page 4 of 10 8 5 1 8 5 2 I45 KJN Standard A 50 Digest 1 0mL of above intermediate standard and dilute to 20mL with Nano water This solution is stored at 4 for up to one month Working Standards Solutions are stored at 4 for up to 2 weeks 8 5 2 1 CCV 2 0 mg L standard 400uL of 50ppm Intermediate into 10mL of digested digestion reagent 8 5 2 2 ICV 1 0 mg L standard 200 uL of 50ppm Intermediate into 10mL of digested digestion reagent 8 5 2 3 RL Check 0 1 mg L standard 0 5 mL of 2ppm CCV into 10mL of digested digestion reagent 8 6 Stock sodium hydroxide 1096 w v 8 6 1 8 6 2 8 6 3 8 6 4 Sodium hydroxide NaOH 50 g Dilute to 500 mL with DI water Dissolve 50 g sodium hydroxide pellets in 400 mL ammonia free deionized water Caution the flask will become warm Cool and dilute to 500 mL Store at room temperature for up to six months 8 7 Mercury II sulfate solution 8 7 1 oo oO AUN oh M 8 7 5 8 7 6 Red mercury II oxide HgO 8g 20 v v sulfuric acid see below 50 mL Dilute to 100 mL with DI water Prepare 20 v v sulfuric acid by carefully adding 20 mL concentrated sulfuric acid to about 70 mL deionized water Caution the container will become hot Swirl co
297. monyl Tartrate solution and 15mL Ammonium Molybdate solution Add the contents of This will make 100mL 9 3 5N Sulfuric Acid 9v 3s 9 4 Ammoniu 9 4 Start with 430mL of slowly with stirrin concentrated H2804 500mL Store in a gl temperature for up t Dissolve 20 g of Am hydrate NHq 6Mo702 water Store ina gl temperature for up t beaker 1 to beaker 2 P Reagent nanopure water and g add 70mL of Let cool and dilute to ass bottle at room O one year m Molybdate solution monium Molybdate 4 4H50 in 500mL nanopure ass bottle at room o three months 9 5 Potassium Antimonyl Tartrate Hemihydrate Qo Sd Dissolve 1 3715g K S nanopure water Dil glass bottle at room six months bO 1 2H50 in 400mL ute to 500mL Store in a temperature for up to 9 6Calibration Standards for Curve 9 6 1 9 6 21 Stock KH PO previously dried in a 105 C oven and stored ina ntermediate 1000ppm 9 6 3 into 1L of Nanopure temperature This st to 12 months or repl with QC samples indi Working Standards desiccator Weigh up 4 3949 KH PO Keep at room andard may be kept for up aced sooner if comparison cate a problem Revision 5 0 OP Page 5 of 9 127 9 6 3 1 Pipette 1mL of 1000ppm PO4 P 9 6 3 2 Analyze various amounts 9 7 Laboratory 9 6 4Stock Non calibrat previously dried in in a
298. mple matrix duplicate or a sample duplicate may be analyzed as well Acceptance ranges are generated from historical data and updated periodically or a range of 70 130 for aqueous samples and 50 150 for solid and sludge samples is used until historical data can be generated If recovery of gt 20 of the analytes falls outside the control limits that LFSM is judged out of control and a follow up must be performed on that sample The RPD must also pass based on historical limits or lt 40 until enough date is acquired to generate these limits An MDL study is completed upon initial set up of the method and whenever major equipment or procedural changes are made Standards are spiked at 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be 2 2 times the reporting limit Analyst Demonstration of Capability 10 9 1 10 9 2 Initial Demonstration of Capability 10 9 1 1 Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed Select a concentration 10 50 times the estimated MDL or midrange and analyze 4 aliquots For aqueous studies spike the selected concentration in reagent water and for non aqueous studies spike in sodium sulfate Analyze each aliquot according to procedures beginning in Sect 11 A cell change may be performed in lieu of an IDOC See ESP SOP Q01 10 9 1 2 For e
299. mples per matrix type This check is made from a noncalibration source Calculate accuracy as percent recovery using the following equation LFB LRB where R percent recovery LFB laboratory fortified blank LRB laboratory reagent blank s concentration equivalent of analyte added to fortify the LBR solution If the recovery of any analyte falls outside the required control limits of that analyte is judged out of control and the source of the problem should be identified and resolved before continuing analyses The laboratory must use LFB analyses data to assess laboratory performance against the required control limits of 85 115 When sufficient internal performance data become available usually a minimum of twenty to thirty analyses optional control limits can be developed from the mean percent recovery x and the standard deviation S of the mean percent recovery These data can be used to establish the upper and lower control limits as follows UPPER CONTROL LIMIT x 3S LOWER CONTROL LIMIT x 3S The optional control limits must be equal to or better than the required control limits of 85 115 The standard deviation S data are used to establish an on going precision statement for the level of concentrations included in the LFB Revision 4 1 120 21 9 5 4 9 5 5 9 5 6 9 5 7 9 5 8 M07 200 7 Calibration Blank A calibration blank is analyzed immediately following daily ca
300. n phosphorus chlorophyll a and dissolved oxygen numeric targets In addition this program will evaluate and determine the relationship between ammonia toxicity and the total nitrogen allocation to ensure that the total nitrogen allocation will prevent ammonia toxicity in Lake Elsinore This component of the nutrient TMDL monitoring program includes the measurement of water quality constituents as listed in Table 3 At a minimum samples will be collected monthly from October to May and biweekly from June to September at three locations stations 1 2 and 3 within Lake Elsinore as shown in Figure 5 Station 4 is an additional station for collection of data for use by UCR students Table 3 Lake Elsinore Parameters to be Monitored water temperature total suspended solids TSS specific conductance chemical oxygen demand COD pH biochemical oxygen demand BOD dissolved oxygen DO total organic carbon TOC total organic nitrogen dissolved organic carbon DOC dissolved organic nitrogen total dissolved solids TDS co nitrite nitrogen NO3 N NO gt turbidity ammonia nitrogen NH N water clarity Secchi depth total nitrogen TN chlorophyll a total inorganic nitrogen TIN oxidation reduction potential total phosphorus TP total iron soluble reactive phosphorus SRP ortho P dissolved iron Fe diss total organic phosphorus dissolved organic phosphorus Lake Els
301. n verification checks or a new calibration Any analyzed samples that were not bracketed by working QC must be reanalyzed If a continuing calibration verification check at the end of the run is out of range during an automated analysis it is likely that the problem will be discovered after the run is completed Upon discovery if the instrument has been idle and it is believed that conditions of the instrument have not changed the analyst may reinject the continuing calibration verification check If this check is successful the run is considered valid If this check is not successful the analyst must take corrective action and perform either two consecutive successful calibration verification checks or a new calibration After that any analyzed samples that were not bracketed by working QC must be reanalyzed Any data deemed reportable by management that is associated with a failed continuing calibration check must be flagged with the proper qualifier NCALh or NCALI on specific analyte Revision 7 0 Q06 Page 8 of 11 5 5 Under the following circumstances results may be reported 5 5 1 Ifthe failed continuing calibration check has a high bias samples that are non detects may be reported without a qualifier 5 5 2 Ifthe failed continuing calibration check has a low bias samples that have a result greater than the maximum regulatory result may be reported with a qualifier 5 6 Organic analyses with gt seven analytes 5 6 1
302. n 8 2 1 MS 0 5ppm 2mL of 100ppm LCS Stock The digest is usually diluted 5 times prior to analysis Revision 5 0 Page 7 of 10 9 3 9 4 9 5 I45 KJN 9 2 3 Add 20mL of digestion reagent 9 2 4 Continue digest starting in section 9 1 4 9 2 5 After digestion while samples are still warm bring up to 80mL with Nanopure and spin with vortex to mix 9 2 6 Pour into cuvettes cool and analyze on the SEAL Leaf Tissue N 0 0 bo Lo bo be Lo Wash leaves with D I water Dry in feed oven overnight Grind leaves into a powder Digest sample according to section 9 2 Report result as N Analysis 9 4 1 See SEAL SOP 141 for general operating instructions 9 4 2 Load standard reagents and samples 9 4 3 9 4 4 9 4 5 Choose method TKN Type in sample table After system has stabilized and the heater temperature has reached at least 60 C calibration may begin Calibration 9 5 1 9 5 2 9 5 3 9 5 4 9 5 5 Calibrate the instrument every run or whenever the calibration check indicates a need A 3 point curve including zero is required by method Normally the laboratory performs a 5 point curve plus a blank An acceptable curve yields an r 0 995 or better The Linear Calibration Range is proven with each calibration since 5 points are used and the curve is linear Results are not reported over the highest calibrator see 11 3 Calibration Check Standards Prepare standards at 1 0p
303. n Standard 0 7456 g KCl pre dried in 105 oven dissolved in 1 liter of Nanopure water The adjustment factor is acquired from this reading This solution is stored at room temperature for up to one year 10 2 105 oven from a separate source than the standard dissolved in 1 liter of Nanopure water This 0 01M KCl Lab Control 0 7456 g KCl pre dried in Revision 5 0 Page 3 of 7 I14 solution is stored at room temperature for up to one year This solution is used full strength and diluted 1 1 with Nanopure water to yield a calibration check at two levels 10 3 11 0 Procedure Tq Reagent water Nanopure Waters 21 Make sure electrode is hooked up securely 22 The instrument should be on TO 11 TI Tis 4 Rinse the electrode off with the D 3 Pour samples and standards into clean dry test tubes Place the tubes in a rack Bring all samples and standards to 24 26 C using a water bath Warm tap water of approximately 27 C is added to the rack and cold samples are allowed to reach room temperature Place thermometer in water bath to measure and monitor the temperature wash bottle and dry by shaking and plotting the end 5 Calibration Place the electrode the Calibration standard solution that has been poured into the test tube about full ensuring that the probe does not rest on the bottom of the test tube Im
304. n apparatus If a sample produces a negative peak that is more negative then the reporting limit the sample pH is checked adjusted to pH 2 if needed and reanalyzed 9 0 Calculations 9 1 9 2 9 3 Compute concentration of samples by comparing sample peak areas rather than peak height with the standard curve Enter raw results into the LIMS Preparation aliquots are entered as the initial and final volumes Dilution factors performed after preparation are entered in the DIL column in LIMS The reporting limit is 0 1 mg L Revision 5 0 153 NH3 Page 9 of 10 9 4 Report 2 significant figures 9 5 Inorganic Nitrogen NH3N NO3N NON 10 0 Definitions See SOP Q15 SOP Definitions 11 0 Safety The toxicity or carcinogenicity of chemicals used in this method has not been precisely defined Each chemical should be treated as a potential health hazard and exposure to these chemicals should be minimized A reference file of material data handling sheets is made available to all personnel involved in the chemical analysis See SOP S01 Concentrated Acids and Bases SOP S03 Spill Control Policy 12 0 Corrective Action For Out of Control or Unacceptable Data See SOP Q06 Corrective Action 13 0 Pollution Prevention and Waste Management 13 1 Waste Disposal 13 1 1 Instrument waste is placed in the KjN waste barrel 13 1 2 Sample waste after distillation is placed in the High Acid Concentration Waste
305. n depends on client requests Client specifications for contact are noted on their Chain of Custody forms or on Element LIMS 2 0 Summary of Method 2 1 An 25 uL aliquot of sample is injected into an eluent stream and passed through a series of ion exchangers The system is comprised of a guard column separator column and suppressor device These separate the ions based on their affinity for a low capacity strongly basic ion exchanger They are then directed onto a strongly acidic cation exchanger where they are converted to their highly conductive acidic forms The conductivity of these acid forms is measured Identification is based on retention time Quantitation is based on peak height or peak area 2 2 In order to use this method for solids an extraction procedure must be performed See Sec 11 11 Revision 7 0 119 Anions Page 3 of 15 3 0 Definitions see SOP Q15 for definitions 4 0 Interferences 4 1 Interferences can be caused by substances with retention times that are similar to and overlap those of the anion of interest Large amounts of an anion can interfere with the peak resolution of an adjacent anion Sample dilution and or spiking can be used to solve most interference problems 4 2 The water dip or negative peak that elutes near and can interfere with the fluoride peak can usually be eliminated by the addition of the equivalent of 1 mL of concentrated eluent 7 3 100X to 100 mL of each standard and sample 4 3
306. n is used in all analyses to correct for instrument drift and physical interferences A list of acceptable internal standards is provided in Table 3 For full mass range scans four internal standards are used scandium indium germanium and terbium Internal standards are present in all samples standards and blanks at identical levels This is achieved by directly adding an aliquot of the internal standards to the CAL standard blank or sample solution Method A Sect 10 3 The concentration of the internal standard is sufficiently high that good precision is obtained in the measurement of the isotope used for data correction and to minimize the possibility of correction errors if the internal standard is naturally present in the sample A concentration of 50 and or 16 7ug L of each internal standard is used Internal standards are added to blanks samples and standards in like manner so that dilution effects resulting from the addition may be disregarded See internal standard log for preparation detail 10 4 Calibration Prior to initial calibration set up proper instrument software routines for quantitative analysis The instrument is calibrated using the internal standard routine described above The instrument is calibrated for the analytes to be determined using the calibration blank Sect 7 6 1 and a calibration standard prepared at 10 ug L for all metals except mercury which is at 0 5ug L minimum of three replicate integrations are
307. nalyst is familiar with the retention times on each column and that if any multi component were present it would be detected A full calibration is performed for each multi component analyte detected in the sample Revision 4 0 Page 8 of 16 7 3 4 7 3 5 7 3 6 7 3 7 7 3 8 O54 8081 Separate calibration standards are used for each multi component target analyte e g Toxaphene and Chlordane Analysts evaluate the specific Toxaphene standard carefully Some Toxaphene components particularly the more heavily chlorinated components are subject to dechlorination reactions As a result standards from different vendors may exhibit marked differences which could lead to possible false negative results or to large differences in quantitative results For calibration verification see section 7 4 3 A 2 uL injection volume of each calibration standard is used Calibration factors The calibration factor for each analyte at each concentration the mean calibration factor and the relative standard deviation RSD of the calibration factors are calculated using the formula below for the calculation of response factors 7 3 7 1 Calculate the calibration factor for each analyte at each concentration as Peak Area or Height of the Compound in the Standard Concentration of the Compound Injected 7 3 7 2 Calculate the mean calibration factor for each analyte as m an CE Cheeses ue where n is the number of standards analyzed
308. nd quality control program If an audit discovers any discrepancy the Quality Assurance Managers will discuss the observed discrepancy with the appropriate person responsible for the activity see organizational chart The discussion will begin with whether the information collected is accurate what were the cause s leading to the deviation how the deviation might impact data quality and what corrective actions might be considered The Quality Assurance Managers has the power to halt all sampling and analytical work by both TASK FORCE and contract laboratory if the deviation s noted are considered detrimental to data quality C2 REPORTS TO MANAGEMENT Interim and final reports for TASK FORCE projects will be issued by the TASK FORCE in accordance with the Lake Elsinore and Canyon Lake nutrient TMDLs Santa Ana RWQCB Resolution No RB8 2004 0037 This calls for the submission of an annual water quality report by August 15 of each year beginning August 15 2007 Interim and final reports for SJR Component projects will be issued by the SJRWC in accordance with the Proposition 50 Chapter 8 Planning Grant Agreement This calls for the submission of a quarterly water quality report by the 10 day of the month following the end of each calendar quarter of each year beginning June10 2006 Interim and final reports for SJRIPP projects will be issued by Riverside County in accordance with the Proposition 13 Watershed Protection Grant Program Gra
309. nd recovery is poor from aqueous solution 4 5 3 Naled is converted to Dichlorvos DDVP on column by debromination This reaction may also occur during sample workup The extent of debromination will depend on the nature of the matrix being analyzed The analyst must consider the potential for debromination when Naled is to be determined Revision 4 1 53 8141 Page 4 of 16 4 5 4 Trichlorfon rearranges and is dehydrochlorinated in acidic neutral or basic media to form Dichlorvos DDVP and hydrochloric acid If this method is to be used for the determination of organophosphates in the presence of Trichlorfon the analyst should be aware of the possibility of rearrangement to Dichlorvos to prevent misidentification 4 5 5 Demeton Systox is a mixture of two compounds O O diethyl O 2 ethylthio ethyl phosphorothioate Demeton O and O O diethyl S 2 ethylthio ethyl phosphorothioate Demeton S Two peaks are observed in all the chromatograms corresponding to these two isomers It is recommended that the early eluting compound Demeton S be used for quantitation 4 5 6 Dioxathion is a single component pesticide However several extra peaks are observed in the chromatograms of standards These peaks appear to be the result of spontaneous oxygen sulfur isomerization Because of this Dioxathion is not included in composite standard mixtures 4 5 7 tributyl phosphorotrithioite is a single component pesticide that 15 readi
310. nd then click Done In Data Tool Main click Merge Files 13 6 Make Necessary edits In Data Transfer select the Instrument Data tab Do a print screen of samples and paste on to a Word page and print each page these pages are useful for documenting any needed edits or problems with QC Upon reviewing chromatograms and noting any edits or problems make any sample name or result edits to the appropriate lines in the Instrument Data table Click Refresh Select the Merged Upload tab Remove the lines of samples that should not be entered ex need dilution associated with bad CCV etc When all edits have been made and lines removed click Save Save as the User File from above ex IC WATERTEMP Revision 7 0 119 Anions Page 15 of 15 13 7 Enter Save and QC review Element Laboratory Data Entry Review In Data Entry Review click Open and double click the saved User File ex IC WATERTEMP Click Save Click Query for each analyte to see if there are any red lines QC problems holding time issues etc Make any necessary edits Add appropriate qualifiers where needed 14 0 Corrective Action For Out of Control Or Unacceptable Data See SOP Q06 Corrective Action 15 0 Pollution Prevention and Waste Management 15 1 Instrument Waste is dumped in the sink and neutralized 15 2 SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S07 Pollution Prevention 16 0 Method Performance See Method 300 Tables 3 9 Ou
311. ng analysis Interferences are more completely discussed in section 4 0 The plasma converts metals in the sample from complex molecules to their atomic form and provides energy to excite them Each metal will absorb energy at a specific wavelength Eventually the metal will return to its ground state by emitting the energy it absorbed The ICP uses this emission of energy to quantify each metal Each metal emits light at a different wavelength This is called polychromatic These wavelengths are separated by a monochromater and detected by a photomultiplier tube 3 0 DEFINITIONS 3 1 See SOP Q15 SOP Definitions 4 0 INTERFERENCES 41 Spectral interferences are caused by background emission from continuous or recombination phenomena stray light from the line emission of high concentration elements overlap of a spectral line from another element or unresolved overlap of molecular band spectra 4 1 1 Background emission and stray light are usually compensated for by subtracting the background emission determined by measurement s adjacent to the analyte wavelength peak Spectral scans of samples or single element solutions in the analyte regions indicate not only when alternate wavelengths are desirable because of severe spectral interference but also show whether the most appropriate estimate of the background emission is provided by an interpolation from measurements on both sides of the wavelength peak or by the measured emission
312. ng is required a stronger acid and heat may be used Always ensure that all acid is thoroughly removed from the bottle prior to use 11 Calculations 11 1 The number of milliliters used for the titration is the Dissolved Oxygen content of the sample in mg L for a 200 ml sample 11 2 The probe is calibrated daily so the reading is the Dissolved Oxygen Content of the sample in mg L 12 Reporting 12 1 Reporting Units mg L 122 Reporting Limits 0 1 mg L 13 Definitions See SOP Q15 SOP Definitions 14 Pollution Prevention and Waste Management 14 1 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S07 Pollution Prevention 15 Quality Control Note See also ESB SOP QO1 for general QC requirements 15 1 Duplicates are analyzed if provided Results must be within 0 2 mg L 15 2 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by Winkler and probe analysis on four replicates of buffered reagent water Acceptance criteria is a maximum RSD of 10 15 3 See SOP 105 for further BOD quality control and corrective action Revision 4 0 124 DO Page 6 of 6 16 References Method Source Note italicized items are an indication of a variation from the method 16 1 Standard Methods AWWA APHA WEF 18th edition method 4500 O C and G
313. nitial calibrations are performed daily or when continuing calibration checks are out of the control limits as specified by the method or SOP Continuing Instrument Calibration Checks CCV 3 7 If an initial calibration is not performed a continuing calibration check is analyzed to verify the existing calibration prior to sample analysis Revision 7 0 Page 10 of 14 S n2 3 7 3 001 Laboratory policy requires that every result reported from instrumental analysis be bracketed with working QC This may be a continuing calibration check If continuing calibration checks are outside acceptance criteria see SOP Q06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager 3 8 Acalibration check standard at the reporting limit may be analyzed at the end of an automated run This standard is used to validate ND results should the LCS ICV or CCV be biased low by demonstrating that the instrument signal at the RL is greater than the method blank signal 3 9 Data reported outside the calibration range is flagged as such NOcal 3 10 Data associated with an unacceptable calibration coefficient or response factor is not reported 4 0 Method Detection Limit Studies 4 A Method Detection Limit Study MDL is completed when there is a significant change in the test method or instrument type 4 1 1 A column of a different phase constitutes a signi
314. ns are accounted for in the software Any additional dilutions prior to analysis are accounted for by entering the factors into the software Apply correction factors for any additional dilution of the prepared sample solution to report samples within the verified linear range 12 4 data is sent to the LIMS If an aliquot other than the default volume is used during preparation this variation is documented in the LIMS initial volume If a dilution is made at the instrument the change in internal Revision 4 1 M07 200 7 Page 17 of 21 standard response will automatically adjust the result prior to data transfer To correctly report the MDL and RL the transferred result is divided by the dilution factor and the dilution factor is placed in the LIMS dilution column 12 5 The result labeled in the run as Si is actually a silica SiO2 result and will be entered as such Silicon standards used to calibrate for silica are entered as silica to account for this conversion 12 6 Total Hardness may be calculated from the calcium and magnesium results as follows SM 2340 B X 50 Total Hardness in 20 12 mg eqiv CaCO L 12 7 Exporting and Entering Data ICP OPTIMA 5300DV Element File Utilities Data manager Choose result name Report Use existing design Browse La open Preview gt print Xclose Cancel Export Use existing design Browse Data tool open Next next next Finish Export data Xcl
315. nt exchange with methyl tert butyl ether MTBE and concentration 15g of a soil sample is concentrated down to 5mL of extract 5g of a sludge sample is concentrated down to 5mL of extract Chromatographic conditions are described which permit the separation and measurement of the analytes in the extract by Capillary Column GC with a nitrogen phosphorus detector NPD and confirmation by GCMS DEFINITIONS See SOP Q15 Revision 4 1 53 8141 Page 3 of 16 40 INTERFERENCES 4 1 Method interferences may be caused by contaminants in solvents reagents glassware and other sample processing apparatus that lead to discrete artifacts or elevated baselines in gas chromatograms reagents and apparatus must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks 4 1 1 Glassware must be scrupulously cleaned Clean all glassware as soon as possible after use by thoroughly rinsing with hot water and Alconox followed by three D L rinses Glassware is then rinsed with acetone Prior to and between use syringes are rinsed with the appropriate solvent 4 2 The use of high purity reagents and solvents helps to minimize interference problems 4 2 Interfering contamination may occur when a sample containing low concentrations of analytes is analyzed immediately following a sample containing relatively high concentrations of analytes After the run is completed the analyst will e
316. nt Agreement This calls for the submission of a quarterly water quality report by the 10 day of the month following the end of each calendar quarter of each year beginning October 10 2006 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 40 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE D1 DATA REVIEW VALIDATION AND VERIFICATION REQUIREMENTS Data generated by each project s activities will be reviewed against the data quality objectives cited in Section A7 and the quality assurance quality control practices cited in Sections B5 B6 B7 and B8 Data will be separated into three categories data meeting all data quality objectives data meeting failing precision or recovery criteria and data failing to meet accuracy criteria Data meeting all data quality objectives but with failures of quality assurance quality control practices will be set aside until the impact of the failure on data quality is determined Once determined the data will be moved into either the first or last category Data falling in the first category are considered usable by the project Data falling in the last category are considered not usable Data falling in the second category will have all aspects assessed If sufficient evidence is found supporting data quality for use in this project the data will be moved to the first category but will be flagged with a J as per EPA specifications D2 VALIDATION AND VERIFICATION METHODS All data recor
317. nt analytes that have been subjected to environmental degradation or degradation by treatment technologies These result in weathered multi component mixtures that may have significant differences in peak patterns than those of standards The dual column option is used This option allows a hardware configuration of two analytical columns joined to a single injection port The option allows one injection to be used for dual column analysis Analysts are cautioned that the dual column option may not be appropriate when the instrument is subject to mechanical stress many samples are to be run in a short period or when contaminated samples are analyzed This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatographs GC and skilled in the interpretation of gas chromatograms Each analyst must demonstrate the ability to generate acceptable results with this method Extracts suitable for analysis by this method may also be analyzed for organophosphorus pesticides Method 8141 Some extracts may also be suitable for triazine herbicide analysis if low recoveries normally samples taken for triazine analysis must be preserved are not a problem 1 7 The following compounds may also be determined using this method Analytes in parenthesis are not certified by NELAP Compound CAS Registry No Alachlor 15972 60 8 Captafol 2425 06 1 Chloroneb 2675 T1 6 Chloropropylate 5836 10 2 Chlorothaloni
318. nt monitoring program Riverside County Flood Control amp Water Conservation District RCFC will lead the San Jacinto Watershed SJW nutrient monitoring program on behalf of the TASK FORCE and the SJRWC and Mr Steve Clark of RCFC amp WCD staff will serve as its Quality Assurance Manager He will be responsible for all aspects of the SJW nutrient monitoring program including organization and training of field staff scheduling of sampling days data management and quality control and interactions with contract laboratories associated with the SJW nutrient monitoring program Elsinore Valley Municipal Water District EVMWD will lead the Lake Elsinore LE nutrient monitoring program and the Canyon Lake nutrient monitoring program Ms Sarah Garber of MWH will serve as its Quality Assurance Manager Dr Michael Anderson of the University of Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 7 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE California Riverside under contract with EVMWD will be responsible for all aspects of the LE nutrient monitoring program including organization and training of field staff scheduling of sampling days data management and quality control and interactions with contract laboratories associated with the LE nutrient monitoring program The Canyon Lake CL nutrient monitoring program will be managed by Dr Michael Anderson of the University of California Riverside under contract with the SJRW
319. ntent of the digestion reagent is intended to produce a digestion temperature of about 360 to 370 degrees Celsius If the sample contains a very large quantity of salt or inorganic solids that dissolve during digestion the temperature may rise causing pyrolytic loss of nitrogen To prevent this from occurring the analyst may use less sample 5 2 If large amounts of organic matter are present an increase in digestion temperature may also occur To prevent this from occurring the analyst may use less sample volume Revision 5 0 I45 KJN Page 2 of 10 5 3 Be cautious of turbidity that may result in the SEAL tubes from the boiling stones if the digestate is not properly decanted Once the digested KJN samples have been poured into the SEAL tubes discard the remaining digestate to prevent such problems 5 4 The color reaction chemistry for TKN analysis is sensitive to changes in acid concentration in the diluted digests The acid concentration may vary from the nominal value for various reasons Typically observed symptoms are significant change in the calibration absorbance range or excessive upward or downward curvature of the calibration line 6 0 Safety digests must be performed under the hood Take care when removing digests from the Block digester Use gloves and safety goggles Sulfuric acid and Sodium Nitroprusside have the potential to be highly toxic or hazardous See SOP S01 Concentrated Acids and Bases SOP S03 Spi
320. ntial cultivated land as fertilizers are carried into surface waters with storm runoff 1 2 2The increasing phosphorus concentrations in surface water raises the growth of phosphate dependent organisms such as algae and duckweed These organisms use great amounts of oxygen and prevent sunlight from entering the water This is known as eutrophication Revision 5 0 T42 TP Page 2 of10 2 0 Working Range 0 05 1 0mg L 3 0 Summary Ammonium molybdate and antimony potassium tartrate reacts in an acid medium with dilute solutions of phosphorus to form an antimony phospho molybdate complex This complex is reduced to an intensely blue colored complex by ascorbic acid The color is proportional to the phosphorus concentration Only orthophosphate forms a blue color in this test Polyphosphates and organic phosphorus compounds may be converted to the orthophosphate form by nitric sulfuric digestion 4 0 Sample Preservation The samples should be preserved by adding 0 5ml L of 1 1 H2504 as specified in CER part 136 Table Check that the pH is less than 2 Samples may be stored in the refrigerator for up to 28 days 5 0 Interferences 5 1 Copper iron or silicate at concentrations many times greater than their reported concentration in Seawater causes no interference However high iron concentrations can cause precipitation of and subsequent loss of phosphorus 5 2Arsenate is det
321. ntil the unit is turned off 8 1 1 9 Turn off unit when the last sample is finished 8 1 1 10 Pour distillate into SEAL tubes Undistilled samples 8 1 2 1 Filter all samples through 0 45 micron microdisk filters directly into SEAL test tubes unless a dilution is made If a dilution is required dilute sample bring up to 50 mL and filter prior to pouring into SEAL tube If less than 5 ml of sample is used dilute with diluant otherwise D I water may be used 8 1 2 2 Use the following volumes based on sample matrix 8 1 2 2 1 Industrial or Influent Wastewater 2 5mL 8 1 2 2 2 Effluent Wastewater 25 50 mL 8 1 2 2 3 Well water 50 ml 8 1 2 2 4 Solids Make a 1 10 water extract extract and swirl periodically for one hour Filter prior to analysis 8 2 Calibration 8 2 1 8 2 2 8 23 8 2 4 The instrument is calibrated every run when a major instrumentation change is made or when the calibration check fails The analyst first analyzes a 1 0 mg L standard If the initial calibration check ICV is valid within 90 110 of the expected value a new calibration is not necessary If the ICV is out calibrate the instrument Although a 3 point curve is required a 5 point curve plus blank is usually prepared An acceptable curve yields an r 0 995 or better Calibration Check Standard Prepare a 1 0ppm standard to check the calibration Analyze prior to sample analysis every 10 sample Revision 5 Page 8 of
322. o determine whether further concentration of the sample is warranted Identification of mixtures i e Chlordane and Toxaphene is based on the characteristic fingerprint retention time and shape of the indicator peaks and quantitation is based on the height or area under the characteristic peaks as compared to the height or area under the corresponding calibration peaks of the same retention time and shape generated using either external calibration procedures If compound identification or quantitation is precluded due to interference e g broad rounded peaks or ill defined baselines are present cleanup of the extract or replacement of the capillary column or detector is warranted Rerun the sample on another instrument to determine if the problem results from analytical hardware or the sample matrix Watch for possible carry over Studies have shown that no carry over occurs after injection of the high calibration standard Rerun samples at or above the reporting limit that following a sample at this concentration Be mindful of carry over that may happen during the extraction procedure Raw results are sent to LIMS Post extraction dilutions are entered in the dilution column Revision 4 0 O54 8081 Page 13 of 16 7 5 Quantitation of multi component analytes Multi component analytes present problems in measurement See EPA Method 8081A 7 6 for suggestions for handling Toxaphene Chlordane BHC and DDT 7 6 Suggested chromatographi
323. od blank is not appropriate and will not be analyzed e g pH flashpoint etc A batch is acceptable if method blanks meet acceptance criteria stated in each analytical SOP Blanks cannot be more negative than batch acceptance criteria If the blank is unusually high or negative troubleshooting must be performed to eliminate the source of contamination before continuing with the analysis See SOP 06 for further corrective action requirements If it is still unclear how to proceed discuss the problem with the supervisor or QA Manager Method blank results greater than or equal to batch acceptance criteria must not exceed a concentration greater than 1 10 of the measured raw concentration of any sample in the associated sample batch Travel Blanks If provided travel blanks must be analyzed whenever a drinking water sample has a result at or above the reporting limit or a liquid sample has a reportable result less than10 times the reporting limit Certain commonly occurring analytes i e PCE TCE THMs HAAs MtBE may be considered an exception See specific method SOP If analyte is present in the travel blank at or above the method reporting limit attach the proper qualifier NTBcv to corresponding sample analytes If analyte 15 not present in the travel blank at or above the method reporting limit attach NTBnd to the sample or analyte where applicable 1 3 Matrix Spikes MS or Laboratory Fortified Sample Matrix LFSM 1 3 1
324. of 10 6 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or Revision 5 0 42 Page 10 of10 equal to 20 Performance Evaluation Studies are performed twice a year 13 0 Calculations 1321 For Total Phosphorus 13 1 1 Convert Absorbance to concentration by plugging spectrophotometer reading into regression equation Do not report results higher than the highest calibrator Talaz Enter initial digestion volume used for samples on the Bench Sheet 13 1 3 Enter raw result into the LIMS 13 1 4 If the digest requires further dilution this value is entered in the DIL column of LIMS Results are reported in mg L to 2 significant figures L3 1 6 Results below 0 05mg L are reported as ND Lasz Other Forms of Phosphorus T3932 Total Dissolved Phosphorus TPD Sample is filtered thru a 0 45micron filter prior to analysis To test the filters include a blank with the analysis that has also been filtered 13 2 2 Total Insoluble Phosphorus TPI Total Phosphorus minus Total Dissolved Phosphorus 13 22 43 Organic Phosphorus O
325. of D I water 7 0 Reagents and Consumable Materials 7 1 Sample bottles Glass or polyethylene sufficient volume to allow replicate analyses of anions of interest 7 2 Reagent water Nanopure free of the anions of interest Water should contain particles no larger than 0 20 microns with a conductance of 0 1uS cm Revision 7 0 119 Anions Page 5 of 15 7 3 Eluent solution Dissolve 0 571 g sodium bicarbonate NaHCO and 0 763 g of sodium carbonate NaCO in 1 liter of nanopure water 7 2 and dilute to 4 liters Store at room temperature for up to 6 months 7 4 Stock standard solutions 1000 mg L and 10 000 mg L solutions Stock standard solutions are purchased as certified solutions Store standards at 4 C until manufacturer specified holding date Once opened the expiration date is 1 year from date opened as long as this does not exceed manufacturer s original expiration date 7 5 Working standard solutions See section 9 5 for concentrations and recipes Working standards are stored at room temperature Calibration standards are stored for up to 3 months LCS solutions are prepared weekly 8 0 Sample Collection Preservation and Storage 8 1 Samples are collected in scrupulously clean glass or polyethylene bottles 8 2 Sample preservation and holding times for the anions that can be determined by this method are as follows Analyte Preservation Holding Time Chloride None required 28 days Fluoride None required 28 da
326. ol to room temperature and dilute to 100 mL Dissolve 8 g red mercury II oxide HgO in 50 mL 20 v v sulfuric acid and dilute to 100 mL with deionized water Filter this reagent Store at 4 for up to three months 8 8 Digestion reagent 8 8 1 OO Un gt 8 8 8 8 8 8 6 Potassium sulfate K2S04 133 g Concentrated sulfuric acid H2SO4 200 mL Mercury II sulfate solution above 25 mL Dilute to 1 L with DI water Add 133 g potassium sulfate K2SO4 to about 700 mL of deionized water and carefully add 200 mL concentrated sulfuric acid H2SO4 Caution the container will become hot Add 25 mL filtered mercuric sulfate solution and dilute to 1 Liter Store at room temperature for up to six months 8 9 Alkaline EDTA 90 90 90 oo 0 AUN 8 9 5 Ethylenediaminetetraacetic acid disodium salt dihydrate 2 5 g Sodium hydroxide NaOH 10 0 g Dilute to 500 mL with DI water To a 500 mL volumetric flask add 2 5 g disodium EDTA dehydrate ethylenediaminetetraacetic acid disodium salt dihydrate and 10 0 g sodium hydroxide pellets NaOH Stir to dissolve Dilute to the mark with ammonia free deionized water Store at room temperature for up to six months Revision 5 0 145 Page 5 of 10 8 10 Stock sodium potassium tartrate solution 1096 w v 8 10 1 Sodium potassium tartrate 50 g 8 10 2 Dilute to 500 mL with DI water 8 10 3 To prepare this reagent dissolv
327. olab cast was made at the time of the sample collection and whether the sample is a field split duplicate An example San Jacinto Storm Event Field Data Form is included as Attachment 1 Additional details of this program element can be found in the Appendix D Lake Elsinore Canyon Lake TMDL Compliance Program San Jacinto River Watershed Sampling Plan In situ measurements of in lake water quality made using the Hydrolab will be recorded in a daily Field Log form Entries will include the date names of sampling personnel weather conditions site number time of sampling depth temperature DO concentration pH EC chlorophyll concentration turbidity Secchi depth and the signature of the sampler An example In Lake Sampling Field Log Form is included as Attachment 2 Field documentation will be completed using indelible ink with any corrections made by drawing a single line through the error and entering the correct value Samples will be delivered to the laboratory at the end of the sampling event to initiate processing within 24 hours The Chain of Custody form will also be required for samples prepared for laboratory analysis The Chain of Custody form will identify the sample number sampling location description date time sample type number of containers tests required and relinquishing signatures example Chain of Custody Form is included as Attachment 3 Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 31 Lake Elsinor
328. ompounds and 100ppb 500ppb 1000ppb 2000ppb 3000ppb and 4000ppb for multipeak compounds 5 5 1 1 Single Peak Compounds 5 5 1 1 1 Intermediate Standard 1000ppb pesticide standard diluted from individual stock standard vials into 90 hexane 10 acetone 5 5 1 1 2 Working Standards Dilute the following aliquots of 1000ppb Intermediate standard including surrogate into 10 mL of hexane 10uL 250uL 500uL 1000uL 2 5 mL and 5 0mL 5 5 1 2 Multiple Peak Compounds 5 5 1 2 1 Intermediate Standard Analyte 4ppm Surrogate 0 2 ppm Standard diluted by taking 0 4 mL of analyte stock at 100ppm and 2 uL of surrogate at 100ppm into 10 mL of hexane 5 5 1 2 2 Working Standards Dilute the following aliquots of Intermediate standard into 10 mL of hexane 1 mL 0 75 mL 0 5 mL 0 25 mL 0 125 mL and 0 025 mL 5 5 2 LFB MS ICV 5 5 2 1 Pesticides Spiking Standard 1 25ppm Dilute 0 5 mL of 250ppm stock standard into 100 mL of methanol Spike 400 uL into 1L of sample or Nanopure for a final concentration of 50 ppb in the extract Spike 200 uL into 5g or 15g of sample or blank sand for a final concentration of 50ppb in the extract 5 5 2 2 Chlordane or Toxaphene 10ppm Dilute 1 mL of 1000ppm stock standard into 100 mL of methanol Spike 200 uL into 1L of sample or Nanopure for a final concentration of 2000 ppb in the extract Spike 1 mL into 5g or 15g of sample or blank sand for a final concentration of 2000ppb in the extract 5 5 3 Endrin DDT Degra
329. on is observed in the EC MUG tube and the tube fluoresces in UV light the sample is considered positive for E coli 3 0 Definitions See SOP Q15 SOP Definitions Revision 6 0 B02 MTF Page 2 of 9 4 0 Interferences 4 1 Ifthe sample is not adequately shaken before portions are removed or if clumping of bacterial cells occurs the MPN value will be an underestimate of the actual bacterial density 4 2 Turbidity See sections 11 2 and 11 2 4 3 An arbitrary 48 hour limit for observation doubtless excludes occasional members of the coliform group that grow very slowly 4 4 Even when five fermentation tubes are used the precision of the results obtained is not of a high order Consequently exercise great caution when interpreting the sanitary significance of coliform results obtained from the use of a few tubes with each sample dilution especially when the number of samples from a given point is limited 5 0 Safety 5 1 When dealing with bacteriological testing it is important to ensure that all working surfaces are clean Gloves are recommended to protect the analyst from exposure to bacteria 6 0 Equipment and Supplies 6 1 Media tubes with Durham tube inserts see ESB SOP section 6 0 for washing instructions 6 2 Metal racks 6 3 Glass Pipets 10mL 6 3 1 Pipets are placed in disinfectant and then washed thoroughly with D I water and then sterilized in a drying oven overnight 6 4 Transfer loops sterilized in a dr
330. on one side or the other The location s selected for the measurement of background intensity are determined by the complexity of the spectrum adjacent to the wavelength peak The selected location s used for routine measurement are free of off line spectral interference interelement or molecular or adequately corrected to reflect the same change in background intensity as occurs at the wavelength peak 4 1 2 Spectral overlaps may be avoided by using an alternate wavelength or can be compensated for by equations that correct for interelement contributions which involves measuring the Revision 4 1 M07 200 7 Page 4 of 21 interfering elements On line spectral interferences observed for the recommended wavelengths are given in Table 3 When operative and uncorrected these interferences will produce false positive determinations and be reported as analyte concentrations The interferences listed are only those that occur between method analytes 4 3 When determining trace analytes the analyst is aware of potential spectral interferences and makes correction where necessary by calculating the interference factor and utilizing a computerized correction routine or utilizing another wavelength 4 4 The interference effects are evaluated for each individual instrument whether configured as a sequential or simultaneous instrument Interferences are specific to the instrument and operating conditions The analyst is required to determine
331. onfiguration and operating conditions satisfy the analytical requirements and to maintain quality control data verifying instrument performance and analytical results Instrument operating conditions which were used to generate precision and recovery data for this method are included in Table 6 10 2 Precalibration routine 10 2 1 Initiate proper operating configuration of instrument and data system Allow a period of not less than 30 min for the instrument to warm up During this process conduct resolution checks using the tuning solution If this solution is out perform consult ELAN 6000 or 9000 manual Revision 3 0 M12 200 8 Page 17 of 26 10 2 2 Instrument stability is demonstrated every day by running the tuning solution Sect 7 7 a minimum of five times with resulting relative standard deviations of absolute signals for all analytes of less than 596 Insert the TUNE report with the daily batch reports The tune solution must pass the following criteria ELAN 6000 ELAN 9000DRCe Background 30 cps Mass 220 lt 2 cps Mass 220 Rh sensitivity gt 150 000 cps In gt 300 000 cps Mg sensitivity gt 20 000 cps Mg gt 50 000 cps Pb sensitivity gt 100 000 cps U gt 200 000 cps CeO lt 0 03 lt 0 03 Ba lt 0 03 lt 0 03 If the oxides are high reduce the nebulizer flow If the tune solution still does not pass refer to the ELAN manual for guidance 10 3 Internal Standardization Internal standardizatio
332. ons greater than these are observed flush the instrument with the rinse blank and monitor the responses in the calibration blank 9 4 6 1 If the responses of the internal standards in the calibration blank are within the limit 9 4 6 1 1 And the internal standard in the sample is bias low take a fresh aliquot of the sample dilute by a factor of two to five add the internal standards and reanalyze This procedure is repeated until the internal standard intensities fall within the prescribed window 9 4 6 1 2 And the internal standard in the sample was bias high it may be naturally occurring in the sample Remove the IS and regroup the metals that are affected with the next closest internal standard or if there is not another internal standard dilute as indicated above 9 4 6 2 If after flushing the response of the internal standards in the calibration blank are out of limits terminate the analysis and determine the cause of the drift Possible causes of drift may be a partially blocked sampling cone or a change in the tuning condition of the instrument Note For additional information concerning corrective action for out of control or unacceptable data see SOP Q06 Corrective Action 10 CALIBRATION AND STANDARDIZATION 10 1 Operating conditions The analyst is advised to follow the recommended operating conditions provided in the ELAN 6000 and 9000 manual It is the responsibility of the analyst to verify that the instrument c
333. or each batch analysis 9 2 25N Sulfuric Acid Slowly with stirring add 70ml concentrated H5504 to 430ml nanopure water Let cool and dilute to 500ml Reagent is stored in a glass bottle at room temperature for up to one year Revision 5 0 I42 EP Page 4 of10 9 2 3Ammonium Molybdate solution Dissolve 20 g of Ammonium Molybdate 4 hydrate NHq 6Mo7024 4H20 in 500m1 Nanopure water Reagent is stored in a glass bottle at room temperature for up to three months 9 2 4Potassium Antimonyl Tartrate Dissolve 1 3715 g K SbO C H 0 1 2H50 400ml Nanopure water Dilute to 500m1 Nanopure water Reagent is stored in a glass bottle at room temperature for up to six months 9 2 5Mix in a beaker 50ml 5N Sulfuric Acid 5ml Potassium Antimonyl Tartrate solution and 15ml of the Ammonium Molybdate solution To this add Ascorbic Acid solution This makes 100ml P Reagent 9 2 6Let all reagents reach room temperature before mixing Mix in the order given turbidity forms in the combined reagent shake and let stand for a few minutes until turbidity disappears before proceeding The reagent is stable for 4 hours at room temperature If refrigerated the reagent can be kept and used for 3 days assuming all QC samples meet the proper acceptance criteria 9 3 Phenolphthalein indicator Dissolve 1 g of Phenolphthalein in 100ml of reagent alcohol ethyl o
334. or analytes not found in Table 7 the range is set to equal that of a similar poor performing analyte Since our data is compared to performance data developed from single laboratory data certain analytes may be outside the limits however the majority should be within the acceptance limits per 8000B sec 8 4 7 Assessing Surrogate Recovery 10 4 1 Acceptance ranges are generated from historical data and updated periodically in Element When surrogate recovery from a sample or method blank is out of acceptance criteria check calculations to locate possible errors fortifying solutions for degradation contamination and instrument performance If those steps do not reveal the cause of the problem reanalyze the extract or re extract the sample if sample is available 10 4 2 If a blank extract reanalysis re extract fails the recovery criterion the problem must be identified and corrected before continuing 10 4 3 If sample reanalysis re extract meets the surrogate recovery criterion report only this data If sample reanalysis re extraction continues to fail the recovery criterion report all data for that sample with the proper qualifier Assessing the Internal Standard 10 5 1 When using the internal standard calibration procedure the analyst monitors the IS response of all samples during each analysis day The IS response for any sample chromatogram should not deviate by more than 50 from the average area calculated during calibration
335. or final nitrogen N and phosphorus P allocations and compliance with the nitrogen and phosphorus TMDL including the waste load allocations WLAs and load allocations LAs This component of the nutrient TMDL monitoring program includes the measurement of nine water quality constituents as listed in Table 2 sampled at eight intervals across the anticipated storm hydrograph for a minimum of three storm events per year from four locations within the San Jacinto watershed as shown in Figure 4 This includes field parameters not listed in the Basin Plan Amendment Table 2 San Jacinto Watershed Parameters to be Monitored pH ammonia nitrogen NH4 N turbidity total phosphorus TP water temperature soluble reactive phosphorus SRP ortho P total organic nitrogen Org N total suspended solids TSS nitrite nitrogen NO2 N chemical oxygen demand COD nitrate nitrogen NO3 N biochemical oxygen demand BOD Figure 4 San Jacinto Watershed Monitoring Locations 10 Miles Mystic Lake San Jacinto River Salt Creek Lake Elsinore Canyonitaks Alternative 2 TMDL Stations Streams Lakes Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 14 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Implementation of a Nutrient TMDL monitoring program in Lake Elsinore The Lake Elsinore nutrient monitoring program will determine compliance with interim and final nitroge
336. or possible carry over contamination 8 2 Carry over studies are performed on most analyses Revision 7 0 006 Page 10 of 11 8 3 8 4 8 5 8 2 1 level at which carry occurs is proven by the carry over study The carry over study consists of analyzing standards at increasing concentrations until carry over is observed in a blank at the reporting limit 8 2 2 The standard level which produced carry over in the blank is noted by the analyst as the minimum level at which proceeding samples may need to be reanalyzed in future runs Whenever possible follow ups are performed within the holding time However they may be performed past the holding time since the reanalysis is to investigate if carry over is present If reanalysis confirms the presence of the analyte the original within holding time result must be reported If the analyte is not present in the follow up the reanalysis result is reported accompanied by the proper qualifier N HTe or N HTa clearly stating that it was analyzed past the regulatory holding time If the sample is unavailable for reanalysis the analyst must document with the raw data reasons why the sample can not be reanalyzed Results may be reported with the appropriate qualifier Nco If possible carry over has caused a drinking water analyte to be near or above the maximum contaminant limit MCL the result must be verified or the analysis must be canceled and the client notified to resamp
337. orrected before the analysis can continue 12 2 Matrix Spike and Matrix Spike Duplicate Conc least 124 12 0 5ppm MS MSD is analyzed once per batch or 1 for every 20 samples per matrix type whichever is greater T7 If the matrix spike and matrix spike duplicate are not within the control limits of 80 120 with a maximum RPD of 20 the Spikes should be re analyzed A Reagent Blank is digested with each batch and used to zero the instrument 4 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be less than the reporting limit 12 4 1 LOD Verification On a yearly basis a vial of reagent water is spiked at a level of at 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank Or M DL T2 12 response to verify the Level of Detection 5 Demonstration of Capability Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL The average percent recovery of the QC samples must be 80 120 with a maximum RSD
338. ose Xclose Xclose Element Laboratory Data entry review Choose bench sheet Select analytes Create Export double click Yes Xclose Laboratory Data tool clear Browse left Revision 4 1 7 200 7 Page 18 of 21 export double click Browse right Clear Select data PE Winlab final double click Auto select Scan for typos Done Merge files Change analyst Save export double click Yes Xclose Xclose Laboratory Data entry review Open export double click Save ok Select analytes Max page Query Edit Lock Change analyst initials fill cells 12 7 1 Delete calculations from QC and the source sample if not requested by the client ie total hardness total cations sodium percentage caco3 sar Filtered blanks need to be qualified Qbfilt Add qualifier to source sample if the analyte is not requested QC Check for perfect zero 0 could be saturated sample 12 7 2 Qualify 12 7 2 1 Blank A blank that does not meet the criteria must be qualified QBLK A blank does not turn red if the result is too negative The result may not be greater than 1 2 the RL 12 7 2 2 BS ABS that is out of range may be qualified QLMS if the MS or MSD meet the BS criteria If a BS is out of range and can not be qualified the analytes in question must be re analyzed unless the results are ND and the BS is high Qualify analytes NLOhi 12 7 2 3 MS MSD 12 7 2 3 1 If both spikes are red check prep dilution and source sample pr
339. other LCS made at a different concentration is analyzed at the end of the run to verify calibration LCS is analyzed with every batch or one per twenty samples whichever is greater If the lab control does not read within acceptance limits 90 110 re make and read again the lab control still does not read correctly re calibrate the instrument 9 2Analyze a Nanopure blank with every batch or one per twenty samples whichever is greater Results must be below but not more negative than the reporting limit Results should be approximately 0 05 NTU or the 0 85 LCS true value may need to be adjusted Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured raw concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a note If more than one sample tube is used check each one with a method blank 9 3Duplicates are analyzed with each batch or every 10 samples per matrix type which ever is more Results must have a RPD 20 9 4 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration of 0 4 0 9 NTU The average percent re
340. oups of five between calibration checks to prevent a similar drift situation from occurring Revision 3 0 M12 200 8 Page 15 of 26 9 4 Assessing Analyte Recovery and Data Quality 9 4 1 Sample homogeneity and the chemical nature of the sample matrix can affect analyte recovery and the quality of the data Taking separate aliquots from the sample for replicate and fortified analyses can in some cases assess the effect 9 4 2 The laboratory adds a known amount of analyte to a minimum of every 20 routine samples per matrix type per batch When combined with the MSD see section 9 4 5 this constitutes a frequency of 10 In each case the LFM aliquot is a duplicate of the aliquot used for sample analysis and for total recoverable determinations added prior to sample preparation For water samples the added analyte concentration is the same as that used in the laboratory fortified blank Sect 7 9 Over time samples from all routine sample sources are fortified 9 4 3 Calculate the percent recovery for each analyte corrected for background concentrations measured in the unfortified sample and compare these values to the designated LFM recovery range of 70 130 Recovery calculations are not required if the concentration of the analyte added 15 less than 3096 of the sample background concentration Percent recovery may be calculated in units appropriate to the matrix using the following equation where percent recovery C s
341. our raw result noted on your data sheet JD 2 Take the electrode out of the each sample rinse it off with D wash bottle dry off and place in the next sample 211 If the conductivity is very low and if 2 It there is enough sample re rinse th electrode and sample tube with the sample re pour the sample and take another reading is best to store cells so that the 1122 21 electrodes are immersed in D I water Change the water frequently to prevent any growth that may cause electrode fouling The electrodes in cells stored in water will require less frequent replatinization than those that dry out between periods of use Any cell that has been stored dry should be Soaked in distilled water for 24 hours before use to assure complete wetting of the electrodes HMS Solid Add deionized water in a 1 10 ratio with the soil i e 5g of sample to 50mL Revision 5 0 I14 EC Page 5 of 7 water or any ratio that is convenient Document the ratio used on the data page T2592 Allow sample to leach for 1 hour with frequent stirring LEO Follow the procedure in section 11 1 12 0 Quality Control Note See also ESB SOP 001 for general QC requirements 12 1 Duplicate analysis will be run with every analytical batch at a minimum frequency of 1 for every 10 samples per matrix type 12 1 1 The Relative Percent Di
342. overning and or certifying agencies The values and ranges for these samples are completely unknown to anyone in the laboratory The vendor provides final reports to the lab and governing and or certifying agencies These reports give the results and acceptance ranges This report is posted so that every analyst can view his her performance A written response is made to the certifying agency regarding follow up investigations of unacceptable results Revision 7 0 Page 8 of 14 001 2 3 Blind Samples 23 1 2 922 2 3 3 2 3 4 Blind samples are spiked samples or duplicate samples that logged in as if they were normal client samples Blind samples either come from the management or an outside source such as a client or an agency Analysts do not know that blind samples are QC samples If the sample comes from an outside source the laboratory management might not know that the blind samples are QC samples If it becomes necessary to investigate an analytical issue the laboratory management shall periodically log in blind samples as a diagnostic tool 3 0 Instrument Calibrations 3 1 Number of Calibration Points 3 1 1 3 1 2 3 1 3 3 1 4 The minimum number of calibration points is determined by the method If the method does not specify the number of calibration standards required a minimum of 2 points is used For 500 and 600 series methods a three point calibration is recommended for linear
343. oxide species 6 1 6 Samples having high concentrations of elements beyond the linear range of the instrument and with isotopes falling within scanning windows should be diluted prior to analysis Revision 3 0 M12 200 8 Page 7 of 26 6 2 Labware For the determination of trace levels of elements contamination and loss are of prime consideration Potential contamination sources include improperly cleaned laboratory apparatus and general contamination within the laboratory environment from dust etc A clean laboratory work area designated for trace element sample handling is used Sample containers can introduce positive and negative errors in the determination of trace elements by contributing contaminants through surface desorption or leaching depleting element concentrations through adsorption processes reusable labware is sufficiently cleaned for the task objectives Labware is washed thoroughly with acetone laboratory grade detergent and D I and then soaked at least half an hour usually overnight in 1 1 nitric acid followed by rinsing with D I 6 2 1 Plastic ware 50 mL and 10 mL centrifuge tubes metal free plastic 6 2 2 Assorted calibrated air displacement pipetters with metal free tips 7 REAGENTS AND STANDARDS Note standards and reagents are stored at room temperature 7 1 7 2 7 3 Reagents may contain elemental impurities that might affect the integrity of analytical data Owing to the
344. peak pesticides 2 ug kg 150 ug kg Sludge single peak pesticides 6 ug kg 500 ug kg Solid Chlordane Toxaphene 7 40 ug kg 1333 ug kg Sludge Chlordane Toxaphene 20 100 ug kg 4000 ug kg Low end of range depends on the RL The pesticide RL varies among analytes See attached LIMS information for individual RL s Compound CAS Registry No Aldrin 309 00 2 alpha BHC 319 84 6 beta BHC 319 85 7 gamma BHC Lindane 58 89 9 delta BHC 319 86 8 Chlorobenzilate 510 15 6 alpha Chlordane 5103 71 9 gamma Chlordane 5103 74 2 Chlordane not otherwise specified 57 74 9 DBCP 96 12 8 4 4 DDD 72 54 8 4 4 DDE 72 55 9 4 4 DDT 50 29 3 Diallate 2303 16 4 Dieldrin 60 57 1 Endosulfan I 959 98 8 Endosulfan II 33213 65 9 Endosulfan sulfate 1031 07 8 Endrin 72 20 8 Endrin aldehyde 7421 93 4 Endrin ketone 53494 70 5 Heptachlor 76 44 8 Heptachlor epoxide 1024 57 3 Revision 4 0 O54 8081 Page 2 of 16 Hexachlorobenzene 118 74 1 Hexachlorocyclopentadiene 77 47 4 Isodrin 465 73 6 Kepone 143 50 0 Methoxychlor 72 43 5 Toxaphene 8001 35 2 Analytes in parenthesis are not certified by NELAP 1 3 1 4 1 5 1 6 Several multi component mixtures 1 Chlordane and Toxaphene are listed as target analytes When samples contain more than one multi component analyte a higher level of analyst expertise is required to attain acceptable levels of qualitative and quantitative analysis The same is true of multi compone
345. pm and 2 0ppm section 8 5 to check the calibration Analyze prior to sample analysis every 10 samples and at the end of the run to prove that the existing calibration is still valid Results must be within 90 11046 recovery A calibration Blank is analyzed after calibration every 10 samples and at the end Results must be less than the reporting limit A standard at the reporting limit is analyzed at the end of the run This is used to evaluate instrument sensitivity should calibration checks show a low bias and to validate samples reported as none detected This standard should have a signal greater than the method blank Revision 5 0 Page 8 of 10 I45 KJN 10 0 Quality Control Note See also ESB SOP QOI for general QC requirements 10 1 10 2 10 3 Matrix Spikes Matrix Spikes and Matrix Spike Duplicates will be run with every analytical batch and at a minimum of once for every 20 samples per matrix type This satisfies the 1096 frequency requirement of the method They will be compared to acceptance ranges generated from historical data See LIMS for most current limits If they do not fall within the acceptance range the sample must be re analyzed If they still do not fall into the acceptance range the data 15 flagged Laboratory Control A standard from a different source than the calibration standards shall be processed as a laboratory control with each analytical batch One LCS will be run with every analyt
346. pm calibration check is analyzed Results must be within 85 115 of the true value Standards are made from the calibration source intermediate 9 4 7 3 Every 15 samples and at the end of the run a calibration blank is analyzed to monitor drift Results should be less than the reporting limit 9 4 7 4 standard at the reporting limit is analyzed at the end of the run This is used to validate none detected results This standard should have a signal greater than the method blank and ND results See section 8 5 1 for solid calibration information 9 5 Reporting 9 5 1 95 2 9 5 3 9 5 4 9 5 5 Examine each sample report to make sure that the software took the proper average Enter raw data and dilutions into the LIMS Do not report results higher than the highest calibrator Watch for possible carry over by examining multiple injections If subsequent readings decline in concentration the initial result may have been biased by the previous sample Do not include this biased result in the sample average Aqueous results are reported in mg L Solid results are reported as Sludge results are reported as dry weight For DOC analyses the filtered date and time will be entered as the preparation date and time 10 0 Quality Control Note See also ESB SOP 01 for general QC requirements 10 1 LCS One LCS is analyzed every 20 samples per matrix type or once per batch whichever is greater If samples are homogenized th
347. problems 5 0 Apparatus 5 1 Test tube rack from SEAL 5 2 13 x 100mm disposable culture tubes 5 3 SEAL Analyzer 5 4 Whatman 2 and Whatman 4 11 0cm filter paper or Gelmin 0 45 micron disk filters 5 5 100ml beakers 5 6 1 ml 2 ml 5 ml 10 ml and 50 ml pipets 5 7 25 ml 50 ml and 100 ml graduated cylinders 5 8 Distillation apparatus 5 9 VWR boiling chips 26397 409 Revision 5 0 153 NH3 Page 3 of 10 5 10 Antifoaming Agent JT Baker B531 05 Note Rinse all glassware prior to use with three portions of D I water Immediately after use thoroughly rinse with three portions of D I water If glassware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 6 0 Reagents 6 1 6 2 6 3 6 4 6 5 6 6 6 7 6 8 6 9 Reagent Water D I water Diluant or preserved water Add 1ml of Sulfuric acid to 1 L of D I This solution is stored for up to 6 months at room temperature Sodium phenate To a 100 ml beaker add 2g of sodium hydroxide and about 10ml DI Swirl to dissolve and cool to room temperature In the fume hood add 5g of crystalline phenol and swirl to dissolve Transfer to a 50ml graduated cylinder and fill to the mark with DI water Store in the refrigerator for three weeks or until the reagent becomes dark brown Sodium hypochlorite solution bleach
348. r Revision 5 0 I22 NO2 Page 3 of 6 6 3 Stock Standard Solution is stored in the walk in refrigerator until manufacturer specified holding dates Once opened the expiration date is 1 year from date opened as long as it does not exceed mmmanufacturuer s original expiration date Stock standards can be replaced sooner if comparison with QC samples indicate a problem 6 3 1 Stock 41 Purchase 304 ppm certified nitrite nitrogen standard solution 6 3 2 Stock 42 Purchase 1000 ppm certified nitrite nitrogen standard solution 6 4 Working Standard These solutions are prepared daily in D I water 6 4 1 Midpoint Check 0 12mg L 6 4 1 1 Dilute 1 ml of stock standard 41 to 500 ml in a volumetric flask 6 4 1 2 Use 10 mL in the beaker and dilute to 50 mL 6 4 2 Lab Control and Matrix Spike 0 1 mg L 6 4 2 1Dilute 25 ml of stock standard 2 to 500 ml in a volumetric flask 6 4 2 2Use 10 mL in the beaker and dilute to 50 mL 6 4 3 Calibration Standards 6 4 3 1 When a new curve is necessary stock standard 41 is diluted to the necessary concentrations 7 0 Procedure 7 1 Sample Set Up 7 1 1 Use 3 beakers for the blank midpoint check and lab control 7 1 1 1 Add 50 ml of D I water to the first beaker for the reagent blank used to tare the instrument 7 1 1 2 Add 40 ml of water and 10 ml of midpoint working standard to the last beaker in the batch 7 1
349. r interface system from support gases or sample components Most of the common interferences have been identified and these are listed in Table 2 together with the method elements affected Such interferences must be recognized and when they cannot be avoided by the selection of alternative analytical isotopes appropriate corrections must be made to the data Equations for the correction of data should be established at the time of the analytical run sequence as the polyatomic ion interferences will be highly dependent on the sample matrix and chosen instrument conditions In particular the common 82Kr interference that affects the determination of both arsenic and selenium can be greatly reduced with the use of high purity krypton free argon 4 1 4 Physical interferences Are associated with the physical processes which govern the transport of sample into the plasma sample conversion processes in the plasma and the transmission of ions through the plasma mass Revision 3 0 M12 200 8 Page 5 of 26 spectrometer interface These interferences may result in differences between instrument responses for the sample and the calibration standards Physical interferences may occur in the transfer of solution to the nebulizer e g viscosity effects at the point of aerosol formation and transport to the plasma e g surface tension or during excitation and ionization processes within the plasma itself High levels of dissolved solids in
350. r intralaboratory generated data is expected to achieve similar results Refer to Refer to MDL studies Initial Demonstration of Capability Studies and laboratory control charts maintained in the QA Office References EPA SW846 method 9056 EPA Methods for the Determination of Inorganic Substances in Environmental Samples August 1993 Method 300 0 revision 2 1 California Department of Health Services IC Rev 0 Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 01 29 07 Revision 5 0 I22 NO2 Page 1 of 6 Standard Operating Procedure Edward S Babcock amp Sons Date Effective 08 23 06 METHOD 4 Standard Methods 4500 NO B TITLE Nitrogen Nitrite Spectrophotometric 1 0 Scope and Application 1 1 This method is applicable to the determination of nitrite in drinking surface and saline waters domestic and industrial wastes This method may also be used for water extractions of solid materials if both client and regulator agree to this variation 2 The method is applicable in the range from 0 01 to 1 0 mg NO2 N L as proven by a yearly curve The reporting limit is 0 10 mg NO2 N L 1 3 Environmental Relevance 1 3 1Contamination is caused by runoff from fertilizer use leaching from septic tanks Sewage and erosion of natural deposits Nitrites are very soluable and do not bind to soils They are likely to remain in water until consumed by plants or othe
351. r isopropyl Add 100ml nanopure water Indicator is stored in a glass bottle at room temperature for up to six months 9 4 6 N Sodium Hydroxide Dissolve 240 g NaOH into 900ml nanopure water Stir on magnetic stir plate under fume hood Caution sample will become hot fumes are noxious Let cool Dilute to 1 liter Revision 5 0 T42 TP Page 5 of10 Reagent is stored in a Nalgene bottle at room temperature for up to one year 9 5Sulfuric Acid Solution 1 4 Gradually add 100m1 concentrate sulfuric acid to 300ml nanopure water cool Warning solution will get HOT Reagent is stored in a glass bottle at room temperature for up to one year 9 6Instra analyzed Nitric Acid conc Note The curve standards Laboratory control samples and blanks are all made with Nanopure water 9 7 Laboratory Control 0 5ppm 9 7 1Stock 100ppm solution containing organic phosphate purchased from a certified vendor Solution is stored at room temperature until manufacturer specified expiration date Once opened the expiration date is 1 year from date opened 9 7 2Working LCS 0 5ppm Pipet 50uL of 100ppm Stock standard into 10ml Nanopure water Digest 10ml of Working standard to yield a 0 5ppm LCS 9 7 3Calibration Check 0 25ppm Pipet 25uL of 100ppm Stock standard into 10ml Nanopure water and digest 9 7 4MS MSD 0 5ppm Pipette 50uL 100ppm Stock Standard into 10ml of
352. r organisms 1 3 2Nitrite N has a MCL of 1mg L and is the etiologic agent methemoglobinemia 2 0 Summary of Method 2 1 The diazonium compound formed by diazotation of sulfanilamide by nitrite in water under acid conditions is coupled with N 1 naphthyl ethylenediamine dihydrochloride to produce a reddish purple color which is read in a spectrophotometer at 543 nm 3 0 Sample Handling and Preservation 3 1 Samples should be analyzed as soon as possible They may be stored for 24 to 48 hours at 4 C Never use acid preserved samples 4 0 Interferences 4 1 There are very few known interferences at concentrations less than 1 000 times that of the nitrite however the presence of strong oxidants or reductants in the samples will readily affect the nitrite concentrations Revision 5 0 I22 NO2 Page 2 of 6 4 2 High alkalinity gt 600 mg L will give low results due to a shift in pH The ideal pH for nitrite analysis is 5 9 After our initial sample dilution of ten with D I it is unlikely that any sample will need pH adjustment Upon review of data should the supervisor observe an alkalinity of 6000 or a pH outside the range the sample pH will be adjusted to 6 with 1 3 HCl and the nitrite reanalyzed 4 3 NC13 imparts a false red color when color reagent is added 3 4 4 The following ions cause precipitation Sb Au Bi Be Pb Hg w Agd and
353. r other obvious abnormalities and instrument performance If those steps do not reveal the cause of the problem reanalyze the extract Revision 4 0 O54 8081 Page 15 of 16 8 5 8 6 8 7 8 8 8 9 8 4 2 Ifa blank extract reanalysis fails the recovery criterion the problem must be identified and corrected before continuing 8 4 3 If sample extract reanalysis meets the surrogate recovery criterion report only data for the reanalyzed extract If sample extract reanalysis continues to fail the surrogate recovery criterion report all data for that sample as suspect 8 4 4 See LIMS for most current historical limits ASSESSING LABORATORY PERFORMANCE LABORATORY FORTIFIED BLANK 8 5 1 laboratory fortified blank LFB and duplicate are analyzed with every twenty samples or one per sample set all samples extracted within a 24 h period whichever is greater The analyst fortifies Nanopure water for aqueous batches and sand for nonaqueous batches Acceptance ranges are generated from historical data See LIMS for most current limits 8 5 2 ALCS is acceptable if 80 or more of the LCS analytes fall within the laboratory prescribed acceptance criteria If this criteria is not met the batch is judged to be out of control and the source of the problem should be identified and resolved before continuing analyses An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at a concentration
354. r the measurements 7 2 1 7 2 2 7 2 3 7 2 4 7 2 5 If a sample is of biological origin or contains high molecular weight materials the use of Method 3640 GPC cleanup pesticide option is recommended Frequently one of the adsorption chromatographic cleanups alumina silica gel or Florisil may also be required following the GPC cleanup Method 3610 alumina may be used to remove phthalate esters Method 3620 Florisil may be used to separate organochlorine pesticides from aliphatic compounds aromatics nitrogen containing compounds Method 3630 silica gel may be used to separate single component organochlorine pesticides from some interflerants Elemental sulfur which may be present in certain sediments and industrial wastes interferes with the electron capture gas chromatography of certain pesticides Sulfur should be removed by the technique described in Method 3660 7 3 Calibration 7 3 1 7 3 2 7 3 3 The method requires a five point calibration for a linear first order model six point calibration for a quadratic second order model and seven point for a polynomial third order model The lab generally calibrates with 6 7 standards A calibration is performed for single component analytes whenever a CCV indicates a new calibration is needed Each run begins with a low level calibration check for each multi component analyte This is intended to demonstrate that the pattern is recognizable the a
355. rated Sulfuric Acid 9 6 Standard Sodium Thiosulfate Titrant Hypo Dissolve 6 205 g Na25503 5H20 in 1 liter Nanopure water Add 4 pellets 0 4 g of NaOH This titrant is standardized against a Potassium bi iodate standard and is made fresh every month 9 7 KI crystals 9 8 Standard Potassium bi iodate solution 0 0021M Dissolve 812 4 mg KH IO3 5 in distilled water and dilute to 1000 ml This standard is stored at room temperature and replaced every 6 months Standardization Dissolve approximately 2 g KI in an Erlenmeyer flask with 100 to 150 ml distilled water Add 1 ml 6 N Sulfuric acid or a few drops of concentrated Sulfuric acid and 20 ml of the standard bi iodate solution Dilute to 200 ml and titrate the liberated iodine with thiosulfate titrant adding starch towards the end of the titration when a pale straw color is reached When the solutions are of equal strength 20 ml of Sodium thiosulfate should be required to titrate the 20 ml of standard bi iodate solution If not adjust the Sodium thiosulfate to match the standard bi iodate Procedure 10 1 Winkler Titration 10 1 1 Start with a 300 ml BOD bottle filled with sample to the top with no air bubbles 10 1 2 Using a buret add 1 ml Manganese Sulfate solution and 1 ml Alkali Iodide Azide solution to BOD bottle 10 1 3 Place the stopper carefully in the bottle to exclude any air bubbles 10 1 4 Mix each bottle by inverting a few times 10 1 5 When floc
356. rces of interference in this method can be grouped into three broad categories 3 1 1 Contaminated solvents reagents or sample processing hardware 3 1 2 Contaminated GC carrier gas parts column surfaces or detector surfaces 3 1 3 Compounds extracted from the sample matrix to which the detector will respond 3 1 4 Interferences co extracted from the samples will vary considerably from waste to waste While general cleanup techniques are referenced or provided as part of this method unique samples may require additional cleanup approaches to achieve desired degrees of discrimination and quantitation Interferences by phthalate esters introduced during sample preparation can pose a major problem in pesticide determinations 32 These materials may be removed prior to analysis using Method 3640 Gel Permeation Cleanup or Method 3630 Silica Gel Cleanup 3 2 2 Common flexible plastics contain varying amounts of phthalate esters which are easily extracted or leached from such materials during laboratory operations 3 2 3 Cross contamination of clean glassware routinely occurs when plastics are handled during extraction steps especially when solvent wetted surfaces are handled Revision 4 0 O54 8081 Page 4 of 16 3 3 3 4 3 5 3 6 3 7 3 2 4 Interferences from phthalate esters can best be minimized by avoiding contact with any plastic materials and checking all solvents and reagents for phthalate contamination Exhaust
357. rd Dilute 100uL of 40ppm Intermediate Standard into 880uL of MtBE for a final concentration of 4 0ppm Also add 20uL of 250ppm surrogate standard and 8uL of 500ppm internal standard Lab Control Matrix Spike Standard second source Four standards are purchased from Protocol 8140 A 1000 Chlorpyrifos Diazinon Disulfoton Fensulfothion Coumaphos Naled Fenchlorphos Fenthion Revision 4 1 Page 8 of 16 Demeton 8141 A 1000 Azinphos Ethyl Carbophenthion Chlorfenvinfos Demethoate 8141 B 1000 Aspon Chlorpyrifos Methyl Crotoxyphos Dichlorfenthion 8141 D 1000 Atrazine Dichlorvos Dioxathion EPN Ethion Dicrotophos Fonofos Trichlofon Simazine Ethyl Parathion Famphur Monocrotophos Fenitrothion Phosmet Leptophos O53 8141 Malathion Sulfotepp Turbofos Phosphamidon TEPP Thionazin 7 4 4 1 Working Spiking Standard Dilute the following amounts to 50mL with MtBE in a 50mL volumetric flask Protocol Stock Amount Working Concentration Concentration ppm ppm 8140 A 1000 1000 20 8141 A 1000 1000 20 8141 B 1000 1000 20 8141 D 1000 1000 20 Spike ImL of the 20ppm spiking solution into reagent water for aqueous samples sodium sulfate for non aqueous samples or sample for MS The final concentration is 20ppb in the sample and 4000ppb in the extract 7 4 4 2 Initial Calibration Verification Standard Dilute 200uL of 20ppm spiking solution into 780uL of MtBE for a final concentration of 4 0pp
358. rd obtained from a reputable vendor This is a noncalibration source standard The ICV solution is stored in a plastic bottle and analyzed as needed to meet data quality needs See standard log for recipe 7 11 Spectral Interference Check SIC Solution and Blank When interelement corrections are applied SIC solutions are needed containing concentrations of the interfering elements at levels that will provide an adequate test of the correction factors See standard log for preparation information 7 12 Intensity Check Plasma Solution The plasma solution is used for determining the optimum viewing height of the plasma above the work coil prior to using the method The plasma solution tuning solution utilized on the Optima is 10 mg L Manganese per manufacturers instruction PE CH 8 The instrument is subjected prior to analysis to the autotune procedure provided with the software 7 13 Internal Standard A Lanthanum solution is added to all standards and samples See standard log for recipe 7 144 high check is performed with each run to prove linearity Results must be within 90 110 recovery to accept sample with elevated results 8 0 SAMPLE COLLECTION PRESERVATION AND STORAGE 8 1 Prior to the collection of an aqueous sample consideration should be given to the type of data required i e dissolved or total recoverable so that appropriate preservation and pretreatment steps can be taken If properly acid preserved the sample can be
359. re an indication of a variation from the method Approved by Susann K Thomas Date 01 06 06 Revision 5 0 I07 COD Page 1 of 7 Draft Standard Operating Procedure Edward S Babcock amp Sons METHOD SM 5220D Effective Date TITLE Chemical Oxygen Demand Colorimetric ANALYTE COD Chemical Oxygen Demand INSTRUMENTATION Spectrophotometer Genesys 10uv 1 0 Scope and Application 1 1 This method covers the determination of COD in surface waters domestic and industrial wastes 1 2 This method may also be used for solid samples if both client and regulator agree to this variation 1 3 The applicable range of the colorimetric method is 10 500 mg L The reporting limit is 10mg L 2 0 Summary of Method 2 1 Sample blanks and standards in sealed tubes are heated in an oven block digester in the presence of dichromate at 150 C After two hours the tubes are removed from the oven or digester cooled and measured spectrophotometrically at 620 nm 3 0 Sample Handling and Preservation 3 1 Collect the samples in glass bottles if possible Use of plastic containers is permissible if it is known that no organic contaminants are present in the containers 3 2 Samples should be analyzed as soon as possible or preserved with sulfuric acid to a pH lt 2 and maintained at 4 C until analysis Analysis performed on unpreserved samples are qualified N_UNP Analysis must take place within 28 days Samples are kept in plast
360. re analyzing 100 mLs of sample For samples high in dissolved solids thoroughly wash the filter with D I water after the sample has passed through the filter Prolonged filtration times resulting from filter clogging may produce high results owing to Revision 5 0 I31 TSS 2 of 6 Page increased colloidal materials captured on the clogged filter Apparatus and Standards 6 1 Side arm flask of sufficient capacity for sample size selected 6 2 Filtration apparatus Membrane filter funnel with a Gelman type A E glass fiber filter disk with a suitable diameter for the funnel 6 3 Drying oven for operation at 105 C 2 C 6 4 Vacuum aspirator 6 5 Desiccator Check on the desiccant to make sure that it is always blue Replace desiccant when it turns purple 6 6 Balance 58 with a sensitivity of 0 1 mg Calibrated with 0 1 g 5g and 100 g class S weights on a daily basis Calibration must be within 5mg for 5g amp 100g and 0 5mg for 0 1g If values are not within these limits recalibrate the balance 6 7 Filter garages to hold glass fiber filters 6 8 Standard laboratory glassware volumetric flasks graduated cylinders pipets Note All glassware is cleaned immediately prior to and after use by thorough rinsing with three portions of D I water If glassware still appears dirty further steps are taken by use of one of the following Al
361. re specified by the instrument manufacturer SEAL AQ2 Method No EPA 125 A Rev 3 9 0 Procedure 9 1 Digestion 9 1 1 Add 3 4 Hengar Granules use once only 9 1 2 Pipet 5mL of digestion reagent into each tube 9 1 3 20mL of aqueous sample into each block digestion tube or use a dilution as needed The method blank will contain digestion reagent only 9 1 4 sure tubes are dry on the outside surfaces Place digestion tubes into the block 9 1 5 X Flip the stand by switch to On The yellow light will appear It will take about 20 30 minutes to reach 180 C When the red light goes on indicating it has reached temperature press the green Start button The green light will go on Samples will heat for about one hour evaporating the water 9 1 6 When the buzzer sounds press the green start button again and add the cold fingers 1 7 After 1 hours at 380 the buzzer will sound and the block will cool down to 180 8 Remove fingers and digestion tubes 9 After a few minutes while samples are still warm add 19mL of Nanopure to each sample and spin with vortex to mix 1 10 Allow at least 2 hours for the turbidity to settle 11 Pour into cuvettes cool and analyze on the SEAL 1 12 See pages 17 20 in BD 46 User Manual for more details of Block Digestion procedure 9 2 Solid Samples 9 2 1 Weigh up 0 1g of solid sample into digestion vessel 9 2 2 LCS 1 800 uL of 100ppm LCS Stock sectio
362. ree until no visible free liquid is present 7 4 1For samples with a lot of suspended matter a smaller volume of sample 10 50 mL may be used Avoid using less than 10mL less than 10mLs must be used an auto pipette can be used to obtain a representative sample by carefully cutting the tip Verify the accuracy of the altered tip by using the Scale Make sure the tip is rinsed well 7 5 Place samples in 105 C oven for 1 5 hours which is longer than the time proven to be sufficient to bring the sample to a constant weight 7 6 Cool filters in an area free of moisture or contamination for 10 15 min Weigh filters or place in a desiccator until ready to weigh Record the final weight 8 0 Calculation Revision 5 0 Page 4 of 6 A B x 1 000 000 mL of sample used Where A Alternatively 2 The reporting limit for this procedure Weight in grams of filter with in the weight readings points and mul Tare weight in grams of filter you may subtract the without any tiply the difference of 100 mL of sample used 200 mL aliquot is 5 mg L I31 TSS residue and actual numbers decimal by the factor based on a Report all results to three significant figures 4 The differenc result is ntered as the initial raw 5 The dilution factor based on a 200mL sample aliquot 9 0 Quality Control Note 1 is entered into
363. rement is in assessing the potential oxygen demanding load of organic material on a receiving stream This statement applies whether the carbon measurement is made on a sewage plant effluent industrial waste or on water taken directly from the stream In this light carbonate and bicarbonate carbon are not a part of the oxygen demand in the stream and therefore is removed by purging prior to analysis The manner of preliminary treatment of the sample and instrument settings defines the types of carbon that are measured Instrument manufacturer s instructions are followed Sample Handling and Preservation Sampling and storage of samples in glass amber bottles is preferable Sampling and storage in plastic bottles such as conventional polyethylene containers is permissible if it is established that the containers do not contribute contaminating organics to the samples Generally sample are received in new VOA vials 5 2 Because of the possibility of oxidation or bacterial decomposition of some 5 3 6 1 components of aqueous samples the lapse of time between collection of samples and start of analysis should be kept to a minimum Also samples should be kept cool 4 C and protected from sunlight and atmospheric oxygen The sample may be kept for 7 days unpreserved or up to 28 days if acidified pH lt 2 with 2504 If dissolved organic carbon is requested filter sample through a 0 45 micron filter prior to preservation Interference
364. require a separate bottle split out for analyses listed below This will be indicated by a gt Make sure to include the entire Lab Number that subsample was split from including the bottle letter 3 3 If the entire unpreserved sample bottle is preserved for an analysis this is indicated the preservative code only 3 4 sample is not logged in correctly for the type of bottle received Login is informed and a note is made on the Work Order Printout e g rec UNP for received unpreserved 3 5 Samples must be brought to a method specified pH however do not add excessive volumes of preservative as this might dilute the sample Use no more than 20 ml of preservative per quart or liter of sample If the sample is still not at the proper pH note on the Work Order Printout and sample bottle NOT gt 12 lt 2 3 6 Sample compositing will be requested in the notes and needs to be done prior to any analysis of the sample Place a checkmark v next to the note on the Work Order Printout Label the bottle COMP with date and initials and apply the printed label if it is provided Enter this information into the computer in Update Status under comments It is very important that this information be entered into Element as soon as it has been done or directly after the splitting process Go to Update Status under comments and enter COMPOSITED or COMP mmddyyinitials in front of the needs to be composited prior to analysis note 3
365. rest of the batch as follows Samp Conc Samp Abs Conc Single Pt Cal Single Pt Cal Abs Revision 5 0 107 COD Page 6 of 7 12 0 13 0 14 0 Draft 11 4 The method blank is run once a week It must be below the reporting limit Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 the measured raw concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a note 11 5 An MDL study is completed whenever major equipment or procedural changes are made Standards are spiked at the reporting limit or 2 5 5 times the estimated MDL and a minimum of seven replicates is analyzed See QA Manual for calculation Results must be 2 2 times the reporting limit 11 5 1 LOD Verification On an annual basis an aliquot of water is spiked at a level of 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL 11 6 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a concentration 5 50 times the MDL The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 11 7 Demonstrat
366. review sheet 13 0 METHOD PERFORMANCE 13 1 See EPA Method 200 7 for data validation information 14 0POLLUTION PREVENTION and WASTE MANAGEMENT See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S06 Disposal of Chlorinated Solvents SOP S07 Pollution Prevention 15 0 REFERENCE 15 1 U S Environmental Protection Agency Inductively Coupled Plasma Atomic Emission Spectrometric Method for Trace Element Analysis of Water and Wastes Method 200 7 Supplement 1 Rev 4 4 May 1994 Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 09 18 06 Revision 4 1 M07 200 7 Page 20 of 21 Table 2 Estimated Detection Limit ppb SM EPA ESB ESB 200 7 6010 Metal Wavelength DL Est Est Est RL MDL DL DL IDL 2 25 03 2 25 03 Ag 328 07 7 7 7 0 4 7 10 4 Al 396 15 28 100 31 As 188 98 100 42 B 208 89 12 100 10 Ba 233 53 4 20 2 2 Be 313 11 0 7 O3 0 0 18 5 1 7 Ca 317 93 10 10 6 7 1000 50 Cd 228 8 2 7 5 3 6 Co 228 62 7 7 7 0 4 7 10 2 5 Cr 267 72 7 1 7 024 10 1 8 Cu 327 39 97 10 6 5 Fe 238 2 4 6 50 9 1 K 766 49 100 700 1000 130 Li 670 78 4 3 7 2 8 100 100 Mg 285 21 1 6 30 1000 40 Mn 257 61 14 2 1 4 0 93 10 3 Mo 202 03 79 8 5 3 10 1 8 Na 589 59 69 30 1000 50 Ni 231 6 15 15 15 10 10 2 4 Pb 220 35 42 40 42 28 20 15 Sb 206 84 32 30 32 21 100 34 Se 203 99 115 100 46 Tot Si 251 61 26 26 500 33 Sn 189 93 25 100 9 6 Sr 407 77 0 4 0 5 0 28
367. rformed to attempt to determine the cause the cause is not determined or the cause is something that could affect the other samples in the batch the analyses will be re run An MDL study is completed whenever major equipment or procedural changes are made Past studies were performed at 50 mg L Standards should be spiked at 2 5 5 times the estimated MDL A minimum of six to seven replicates is analyzed See QA Manual for calculation Results must be below the reporting limit LOD Verification On a yearly basis a QC sample is Spiked at a level of 2 3 times analyte MDL The sample is analyzed Analyte response must be greater than method blank response to verify the Level of Detection or MDL Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four consecutive replicates of a QC sample made at a concentration of 5 50 times the MDL Past studies were performed at 25 or 50mg L The average percent recovery of the QC samples must be 80 120 with a maximum RSD OE LOs Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet labor
368. rganic Analyses Chlorine is an interferant for almost all organic analytes Dechlorination is handled in the following manner 13 1 Methods 504 8011 524 624 8260 531 and 547 It is more appropriate for Organic analyses to be sampled prior to chlorination therefore that vast majority of our samples are not chlorinated If it is unclear whether a sample will be taken from a chlorinated source the client will be contacted Revision 3 0 A06 Page 6 of 8 for clarification If it is known that a sample will be from a chlorinated source the appropriate sample container will be provided containing the method specified dechlorination salt sodium thiosulfate or sodium sulfite 13 2 Methods 507 8141 508 608 8081 515 8151 525 625 8270 548 As a precaution method specified dechlorination salt is added prior to extraction to drinking water and final effluent samples 14 0 Separate Carts 14 1 The following tests have their own carts When a sample is received requesting only one of these analytes the sample bottle is placed on this special cart 14 1 1 Color Odor and Turbidity A COT is recorded on the bottle cap and Work Order printout 14 1 2 Nitrate A is recorded on the bottle cap and Work Order printout 15 0 Unpreserved Line Up 15 1 The following samples are placed on the unpreserved cart 15 1 1 Unpreserved bottles UNPRES 15 1 2 Dissolved sulfide bottles DH2S should be zero headspace 15 1 3
369. rganochlorine OC pesticides EPA 8081 separate entries 0 01 5 ppb 6 7 pt Curve below Aldrin OC EPA 8081 0 0096 ug L 0 01 5 ppb 6 7 pt Curve a BHC OC EPA 8081 0 015 ug L 0 01 5 ppb 6 7 pt Curve b BHC OC EPA 8081 0 043 ug L 0 01 5 ppb 6 7 pt Curve g BHC Lindane OC EPA 8081 0 021 ug L 0 01 5 ppb 6 7 pt Curve d BHC OC EPA 8081 0 038 ug L 0 01 5 ppb 6 7 pt Curve Chlordane OC EPA 8081 0 045 ug L 0 1 40 ppb 6 7 pt Curve 4 4 DDD OC EPA 8081 0 018 ug L 0 01 5 ppb 6 7 pt Curve 4 4 DDE OC EPA 8081 0 013 ug L 0 01 5 ppb 6 7 pt Curve 4 4 DDT OC EPA 8081 0 018 ug L 0 01 5 ppb 6 7 pt Curve Dieldrin OC EPA 8081 0 012 ug L 0 01 5 ppb 6 7 pt Curve Endosulfan 1 OC EPA 8081 0 011 ug L 0 01 5 ppb 6 7 pt Curve Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 33 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Endosulfan II OC EPA 8081 0 018 ug L 0 01 5 ppb 6 7 pt Curve Endosulfan sulfate OC EPA 8081 0 23 ug L 0 01 5 ppb 6 7 pt Curve Endrin OC EPA 8081 0 013 ug L 0 01 5 ppb 6 7 pt Curve Endrin aldehyde OC EPA 8081 0 056 ug L 0 01 5 ppb 6 7 pt Curve Heptachlor OC EPA 8081 0 01 ug L 0 01 5 ppb 6 7 pt Curve Heptachlor epoxide OC EPA 8081 0 01 ug L 0 01 5 ppb 6 7 pt Curve Hexachlorobenzene OC EPA 8081 0 026 ug L 0 01 5 ppb 6 7 pt Curve Hexachlorocyclopentadiene OC EPA 8081 0 01 ug L
370. rior to analyses conducted by this method 9 2 2 Linear calibration ranges The range at which at the high end the analyte response is not less than 10 below what is expected Our laboratory proves that we are operating within this range by analysis of standards that bracket the concentrations of any analytes reported Analytes that are higher than our highest standard are diluted A 500 ug L and a 100 ug L 2 ug L Hg is used to check upper concentration ranges 9 2 3 Quality control sample QCS or ICV When beginning the use of this method on a quarterly basis or as required to meet data quality needs verify the calibration standards and acceptable instrument performance with the preparation and analyses of a QCS To verify the calibration standards the mean concentration from 3 replicates of the QCS1 prepared to a Revision 3 0 M12 200 8 Page 11 of 26 concentration value of 50 ug L for all metals except Hg which is at 1 ug L Must be within 1096 of the stated QCS value The QCS is used for determining acceptable on going instrument performance the QCS is prepared as stated in section 7 8 and analysis of the QCS must be within 1096 of the stated value or within the acceptance limits listed in Table 8 whichever is the greater If the QCS is not within the required limits an immediate second analysis of the QCS is recommended to confirm unacceptable performance If the calibration standards and or acceptable instrument
371. riteria Relative standard deviation between the four replicates must be less than 20 for Inorganic analyses and less than 40 for Organic analyses The trainer must co initial all work performed during the training period 6 2 Demonstration of Continuing Proficiency DoCP 6 2 1 6 2 2 6 2 3 On an annual basis each analyst or work cell must complete a Demonstration of Continuing Proficiency for every certified analytical procedure performed that year unless they or a member of their cell has performed an IDoC or cell change form that year The demonstration may consist of one of the following 6 2 2 1 Valid LCS data from four consecutive LCS samples 6 2 2 2 Results from a successful Proficiency Testing Study 6 2 2 3 Successful analysis of a blind performance sample on a similar test method using the same technology e g 524 624 and 8260 6 2 2 4 of the above is not practical the analysis of authentic samples that have been analyzed by another trained analyst with statistically indistinguishable results LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 2046 for Inorganic analyses or 4096 Revision 7 0 Q01 Page 14 of 14 for Organic analyses allowing for one marginal exceedance if applicable 7 0 Evaluation of Selectivity 7 1 The laboratory shall evaluate selectivity by following the checks establish
372. rment lactose with gas and acid formation within 48 h at 35 C Results of the examination of replicate tubes are reported in terms of Most Probable Number MPN per 100 mL of sample This number based on certain probability formulas is an estimate of the mean density of coliforms in the sample Coliform density together with other information obtained by engineering or sanitary surveys provides the best assessment of water treatment effectiveness and the sanitary quality of untreated water This method is used for drinking water surface water source water wastewater samples and solids Reporting limit 2MPN 100mL Range 2 1600MPN 100mL 2 0 Summary of Method 2 1 Sample is placed at various dilutions into tubes containing Lauryl sulfate broth and incubated for up to 48 hours at 35 0 5 Each broth tube which shows CO5 formation inside the Durham tube is transferred to a brilliant green bile tube These tubes are incubated at 35 C for a total of 48 hours If gas formation is present in their Durham tubes the sample is considered positive for total coliform bacteria The positive broth tubes are also transferred to E C media wastewaters and source waters or drinking waters The tubes are incubated at 44 5 C 0 2 C for 24 2 hours in the fecal water bath If CO formation is observed in the EC tube after the incubation period the sample is considered positive for fecal coliform bacteria If CO formati
373. rs to be Monitored sese 13 Table 3 Lake Elsinore Parameters to be Monitored essent 14 Table 4 Canyon Lake Parameters to be Monitored sese 16 Table 5 SJRIPP Waste Characterization Table sese 17 Table 6 SJRIPP Constituents to be Monitored esses nen ren rennen nennen nene 17 Table 7 Project Reporting Requirements enne ennt 22 Table 8 San Jacinto Watershed and SJRIPP Sampling Methods eee 26 Table 9 Lake Elsinore and Canyon Lake Sampling Methods eene 29 Table 10 Anayltical Methods San Jacinto Watershed Nutrient TMDL and SJRIPP Monitoring Probram eo eee eee eee et eee roten ste OR Pee etre 32 Table 11 Analytical Methods Lake Elsinore and Canyon Lake Nutrient TMDL Monitoring 35 FIGURES Figure 1 Organizational Chart amp Responsibilities essere 7 Figure 2 Organizational Chart amp Responsibilities essere 8 Figure 3 Organizational Chart amp Responsibilities esee 8 Figure 4 San Jacinto Watershed Monitoring Locations eese 13 Figure 5 Sampling Sites on Lake E smore ii eio ide tg ac tdt dete 15 Figure 6 Sampling Sites Canyon 16 5 1 Example TMDL Field Data Sheet Form 2 Example
374. s Ais Cs where Response for the analyte Ais Response for the internal standard Cis Concentration of the internal standard ug L Cs Concentration of the analyte to be measured ug L 9 3 If the RF value over the working range is constant 20 RSD or less the average RF can be used for calculations Alternatively the results can be used to plot a calibration curve of response ratios A Ajs vs Cs A linear curve must have a correlation coefficient r gt 0 99 A nonlinear curve must have a coefficient of determination r gt 0 99 9 3 1 The above criteria applies to all analytes that appear on the LIMS reporting lists 9 3 2 If due to the long list of compounds every analyte cannot meet one of the above criteria a calibration can be accepted if the mean of the RSD values of all analytes in the calibration is lt 20 If the mean criteria is used instead of individual RSD or coefficients reportable results must be qualified for analytes outside 20 criteria 9 4 Calibration checks are analyzed at the beginning and end of every run and every 12 hours The Initial Calibration Verification Standard is analyzed after the calibration for Revision 4 1 53 8141 Page 10 of 16 validation The continuing calibration check is analyzed every 12 hours and at the end of the run 9 4 1 ICV results must be within 15 of the expected value for each target analyte or the average of all the analyte responses must be within
375. s Carbonate and bicarbonate carbon represent an interference under the terms of this test They are removed by purging the sample with oxygen prior to analysis 6 2 This procedure is applicable only to homogeneous samples which can be injected into the apparatus reproducibly by means of a microliter type Revision 5 0 26 Page 3 of 9 6 3 6 4 syringe or pipette The openings of the syringe or pipette limit the maximum size of particles that may be included in the sample A homogenizer is used to reduce the size of large particles and mix the sample evenly Any contact with organic may contaminate the sample Avoid plastic containers and rubber tubing DOC can be lost on the filter or contaminated from the filter When analyzing for DOC filter a method blank and LCS 7 0 Apparatus 7 1 7 2 7 3 7 4 7 5 Apparatus for blending or homogenizing samples Biospec Tissue Tearer Apparatus for total and dissolved organic carbon Shimadzu TOC Vsch Standard laboratory glassware volumetric flasks beakers graduated cylinders pipets and autosampler vials Glass syringe 0 45 micron disk filters Apparatus for solid samples TOCSSM 5000A Note See instrument manual for maintenance requirements Note glassware is cleaned immediately prior to use with Nanopure water followed by rinsing with TOC Reagent Water section 8 1 After use glassware is cleaned by thorough rinsing with three portions of D I water If gla
376. s adversely affect the colorimetric procedure Prior to NaOH preservation test liquid samples for sulfide by placing a drop of sample on lead acetate paper previously moistened with acetate buffer If paper turns brown sulfide is present Add lead acetate or lead carbonate to the neutralized sample until the sulfide is gone as indicated by retesting Filter the sample before raising the pH for stabilization Place a Pb on the sample cap and on Work Order Printout if treatment was necessary Place a NS on the Work Order Printout if no sulfide was detected Make a lead carbonate blank for the analyst to use as a calibration check In a 500mL volumetric flask add 200mL D I and 5g of NaOH dissolve Add lead carbonate to the volumetric flask replicating the exact amount that was added to the sample per 500mL and bring up to 490 495mL leaving space for the Cyanide analyst to add spiking solution 4 4 1 Lead acetate paper Cut up available filter paper into strips Soak strips in a saturated solution of lead acetate and D I 4 4 2 Saturated lead acetate solution Add lead acetate salt to D I water until solution is saturated and salt will no longer dissolve 4 4 3 Acetate buffer pH 4 SM 4500 243g anhydrous NaC H30 3H50 into 400 mL D I water Add 480 mL acetic acid and bring up to a liter with D I 4 4 4 Above solutions are stored at room temperature for up to one year 4 5 Aldehydes convert cyanide to cyanohydrin that doe
377. s not respond to this method Stabilize all liquid samples with NaOH and add 1ml 35 ethylenediamine solution per 500ml of sample Place an E on the sample and on the Work Order Printout EDA is not necessary for drinking water samples 4 5 1 3596 Solution Dilute 35ml pharmaceutical grade anhydrous NH 2CH2CH2NHz2 to 100ml D I Store at room temperature make fresh monthly Revision 3 0 06 Page 4 of 8 5 0 Phenol 5 1 Samples must be collected in a glass container Preserve samples with approximately 2 mL of 1 1 H2SO0 per liter to pH lt 2 and refrigerated to 4 C 2 C Place an S on the Work Order Printout and sample lid The holding time for Phenols is 28 days If possible screen for chlorine prior to preservation 5 2 Oxidizing agents such as chlorine will oxidize phenols Test each drinking water and final effluent sample by filling a snap cap one quarter full with sample and adding a drop of Orthotolidine Solution A yellow orange color indicates the need for treatment Add sodium thiosulfate a few drops at a time no more than 16mL per liter of sample until a retesting of the sample produces no color change Place an TS on the sample cap and Work Order Printout whenever sodium thiosulfate is used Document amount added on the Work Order Printout Place an X on the Work Order Printout if no chlorine was detected 5 3 Orthotolidine Solution See section 4 3 1 above 5 4 Sodium Thiosulfate Solution See section 4
378. screen for chlorine section 4 3 prior to preservation 4 1 1 35 NaOH 175g NaOH into 500 mL of D I Stored at room temperature for up to one year Revision 3 0 06 Page 3 of 8 4 2 The samples should be stored in a refrigerator or in an ice chest filled with water and ice to maintain temperature at 4 The maximum holding time is 14 days 4 3 Oxidizing agents such as chlorine decompose most of the cyanides Test drinking water and final effluent samples by filling a snap cap one quarter full with sample and adding a drop of Orthotolidine Solution A yellow orange color indicates the need for treatment Add sodium thiosulfate a few drops at a time no more than 16mL per liter of sample until a retesting of the sample produces no color change Place an TS on the sample cap and Work Order Printout whenever sodium thiosulfate is used Document amount added on the Work Order Printout Place an X on the Work Order Printout if no chlorine was detected 4 3 1 Orthotolidine Solution Dissolve 1 35g orthotolidine dihydrochloride into 500 mL D I water Prepare separately a solution of 150 mL 1 and 350 mL D I water always add acid to water Combine the two solutions Stored at room temperature for up to one year 4 3 2 Sodium Thiosulfate solution BOD titrant Dissolve 6 205 g Na2S5203 5H20 in 1 liter Nanopure water Add 4 pellets 0 4 g of NaOH This solution is made fresh every month and stored at room temperature 4 4 Sulfide
379. sed to store samples Each new lot of bottles is tested for trace contaminants by analysis of an acid blank placed in one sample bottle from that lot Results must be below the MDL 7 0 REAGENTS AND STANDARDS 7 1 7 2 7 3 7 4 7 5 7 6 Reagents may contain elemental impurities that might affect analytical data Only high purity reagents that conform to the American Chemical Society specifications 13 should be used whenever possible If the purity of a reagent is in question analyze for contamination All acids used for this method must be purchased from the manufacturer instra analyzed spectro grade Hydrochloric acid concentrated sp gr 1 19 Nitric acid concentrated sp gr 1 41 HNO3 Reagent water All references to water in this method refer to ASTM Type I grade water Our lab uses Nanopure Standard Stock Solutions Stock standards are purchased from a reputable supplier either separately or as mixed solutions Two sources are acquired to verify instrument performance Solutions are stored at room temperature Manufacturer specified holding times are observed Working Standard Solutions Solutions are made from above stock solutions in 5 HCl and 10 HNO3 Solutions are stored at room temperature for up Revision 4 1 M07 200 7 Page 7 of 21 to six months Solutions will be replaced sooner if comparison with QC samples indicate a problem See standard log for recipes Note f the other QC standards
380. sh evaporating dishes with a green scrubbie 1 1 HNO if necessary and plenty of D I Put dishes back in 180 C oven for 1 hour Cool and place in desiccator for the next set 22 5 Solid samples may analyzed by first preparing a 1 10 water extract Add an amount of reagent water equal to ten times the weight of solid material taken as a sample This mixture is agitated for sixty minutes by shaking intermittently Filter the resulting slurry through a 0 45 micron membrane type filter Add filtrate to TDR dish Report result in the extract as mg L attaching qualifier N WXr 11 0 Calculation and Reporting A B x 1 000 000 Revision 5 0 I29 TDS Page 6 of 8 ml of sample used Where A Weight in grams of dish with residue and B Tare weight in grams of dish 11 1 Alternatively you may subtract the actual numbers in the weight readings without any decimal points and multiply the difference by the factor of 100 ml of sample used 11 2 Results are entered into LIMS by taking the Difference from data page X Dilution Factor based on a 200mL default volume 2 The dilution factor is placed in the DIL column to account for initial volume differences The initial and final volumes are set at 200 and 100 mL and are not adjusted by the analyst 1 3 Reporting Units mg L 1 4 Reporting Limit 10 mg L for 200ml aliquot or 20 mg L for 100ml aliquot
381. sion is then installed at the discretion of the network or database administrator The database will be operated with a transaction log recording all changes with ability to roll back if necessary Full database backups will occur on a weekly basis and immediately before batch uploads It is expected TMDL data will be loaded quarterly to twice per year Data will be exported from SAW DMS into the SWAMP format using a pre made query that will map data fields from SAW DMS to the SWAMP template The exported data will then be sent to the SWRCB IM Coordinator for processing into the SWAMP database The data will be retrieved for analysis and report writing by exporting from SAW DMS using pre made queries Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 39 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE C1 ASSESSMENT AND RESPONSE ACTIONS All reviews will be made by the San Jacinto Watershed or Lake Elsinore and Canyon Lake Quality Assurance Managers Quality Assurance Managers and may include the Santa Ana RWQCB Quality Assurance Program Manager The Quality Assurance Managers will conduct reviews of sampling procedures on an annual basis Reviews will be observed practices against those found in this QAPP The Quality Assurance Managers will audit all contract laboratories annually The review will be observed method practices against contract laboratory s SOPs and an audit of data from the contract laboratory s quality assurance a
382. ssion equation See most current curve for proper equation 10 5 Any sample that reads an absorbance above the high standard must be redone at a higher dilution Also any sample that is cloudy or turbid or may cause any colorimetric interference must be diluted 10 6 Immediately after calibration a 250mg L lab control serves as the ICV It must be within 9596 10596 of the expected value or the calibration curve is redone 10 7 See below for CCV information 11 0 Quality Control Note See also ESB SOP 01 for general QC requirements 11 1 The 250mg L lab control is used as a CCV It is analyzed every twenty samples per matrix type or one per analysis batch whichever is greater If recovery is not within 9596 10596 of the expected value either the analysis is repeated or it is recalculated based on a single point calibrator 11 2 A MS MSD is analyzed every twenty samples per matrix type or one per analysis batch whichever is greater The acceptance range is 8096 120 of the expected value and 75946 12046 for solids sludges The relative percent difference between the spikes must be no greater than 2096 11 3 The 500mg L lab control is used as the ending CCV It is analyzed at the end of the batch If recovery is not within 9596 10596 of the expected value a new one is digested and reanalyzed If the redigested CCV fails a 250mg L calibrator is digested from a non LCS source It is used asa single point calibrator to recalculate the
383. ssware still appears dirty further steps are taken by use of one of the following Alconox and hot water 1 1 acid rinse acetone or appropriate solvent rinse Glassware is always finished with a final D I rinse 8 0 Reagents and Standards 8 1 8 2 8 3 TOC Reagent Water Blank solution 1L Nanopure w 1ml HCl Water is stored at room temperature up to one year Inorganic Carbon Purge Blank Carbonate solution Weigh 1 25g of sodium carbonate and transfer into the 1000 mL volumetric flask containing 100 mL of Nanopure water Dissolve and bring up to 1L with Nanopure water Blank is stored at room temperature up to six months Calibration Standards 8 3 1 Calibration Stock Standard Potassium Acid Phthalate purchased from a certified vendor and kept for 10 years 8 3 2 Calibration Intermediate Add 425mg Potassium Acid Phthalate dried ae 105 C for 4 hours to 100ml of TOC reagent grade water This will be equivalent to 2000mg L of organic carbon This solution is stored at room temperature for up to a year 8 3 3 Calibration Working Standards One 7 point calibration curve is prepared The concentrations for the water curve are as follows Omg L 0 3mg L 2mg L 4mg L 7mg L 10mg 1 and 20mg L The concentrations for the liquid curve are as follows Omg L 0 7mg L 2mg L 4mg L 7mg L 10mg L and 20mg L These are prepared by making a 20ppm standard 100ml of 2000ppm calibration standard to 100ml TOC reagent water in a volumetr
384. sults are recorded 12 4 Media Checks 12 4 1 A blank known negative and a known positive culture is analyzed with each set of samples Tubes of Lauryl sulfate broth are inoculated each with E coli and P aeruginosa These are incubated along with the lauryl sulfate broth samples to ensure reproducibility of results This is also done with green bile and incubated along with the green bile tubes to ensure reproducibility Revision 6 0 B02 MTF Page 7 of 9 13 0 Calculation of Most Probable Number MPN 13 1 The most probable number estimates the number of specific bacteria in water and wastewater by the use of probability tables The MPN is based on the number of tubes that have confirmed for or are present for bacteria i e total coliform fecal coliform etc The MPN can also be determined by a combination of confirmed tubes when using multiple dilutions When more than three dilutions were analyzed use the highest dilution that gives confirmed results in all five test tubes along with the next two dilutions Both tables are listed in Standard Methods 18th edition and is based on the amount of bacteria per 100 mL of sample If the combination of positive tubes cannot be found on the MPN charts the MPN can be calculated by the following Number of Positive Tubes X 100 in negative tubes X Vin all tubes This formula was found in Standard Methods 18th edition me of sample 7 ar of sample N 14 0 Method Performance
385. t is generally not significant with finished waters Dirty glassware or sample vibration will cause a positive interferenc 5 0 Apparatus 5 1The 2100N Hach turbidimeter consists of a nephelometer with light source for illuminating the sample a photo electric detector with a readout device to indicate the intensity of light scattered at right angles to the path of the incident light The turbidimeter is designed so that little stray light reaches the detector in the absence of turbidity should be free from significant drift after a short warm up period 5 2The sensitivity of the instrument permits detection of a turbidity difference of 0 05 unit or less in waters having turbidities less than 1 unit The minimum detection level reported is 0 05 NTU The instrument is able to measure from 0 05 to 4000 units turbidity Several ranges are available to obtain both adequate coverage and sufficient sensitivity for low turbidities 5 3The sample tubes are made of clear colorless glass They must be kept scrupulously clean both inside and out and discarded when they becom Scratched or etched They must not be handled at all where the light beam from the instrument strikes them so they are provided with sufficient extra length so that they may be handled at the top Revision 5 Page 3 of 7 54 Da wil l 0 I36 Turbidity fferences in physical design of turbidimeters cause differen
386. t on each batch the original and the RE batch which result will be taken and the reasons why 3 10 2 Approve only the entry lists that are acceptable Cancel all others 3 10 3 If an entire entry list is unacceptable use the mouse to change the Approval Status in the upper right hand corner 3 10 4 Update to cancelled Revision 4 0 Q10 Page 6 of 6 4 Quality Assurance Review 4 1 Log In Review prior to sample analysis checks the following 4 1 1 The list of analyses on the chain of custody is compared to the Log In Sheet to ensure accuracy 4 1 2 All vital information has been accurately transferred into LIMS 4 1 3 Appropriate projects and client specific requests are included in the comments 4 2 Project Manager Review 4 2 1 Client reports for special projects will be reviewed by a project manager 4 2 2 State forms will be reviewed by a project manager 4 2 3 The project manager checks the following 4 2 3 1 Allof the appropriate analyses and analytes are on the final report 4 2 3 2 All required QC is attached QC is acceptable qualifiers make sense etc 4 2 3 3 Adds J flags if requested 4 2 3 4 Checks the comment section in the LIMS review report Ensures that client special requests have been followed such as different reporting limits analyte lists qualifiers etc 5 Final Review 5 1 The final reviewer checks the reports for any apparent mistakes prior to signing Approved by Susann K Thomas Da
387. t recovery for each analyte corrected for background concentrations measured in the unfortified sample and compare these values to the designated LFM recovery range of 70 13096 Recovery calculations are not required if the concentration added is less than 25 of the sample background concentration Percent recovery may be calculated in units appropriate to the matrix using the following equation C s C R x 100 where R percent recovery C s fortified sample concentration C sample background concentration s concentration equivalent of analyte added to fortify the sample 9 6 4 Ifthe recovery of any analyte falls outside the designated LFM recovery range and the laboratory performance for that analyte is shown to be in control Sect 9 3 the recovery problem Revision 4 1 M07 200 7 Page 14 of 21 encountered with the fortified sample is judged to be matrix related not system related The data user should be informed that the result for that analyte in the unfortified sample is suspect due to either the heterogeneous nature of the sample or matrix effects 9 6 5 Laboratory Fortified Matrix Duplicates LFMD or Matrix Spike Duplicates MSD are analyzed every 20 samples per matrix type per sample batch Relative Percent Difference must be 2046 9 6 6 Where reference materials are available they should be analyzed to provide additional performance data The analysis of reference samples is a
388. t water Nanopure 8 0 Colorimetric Procedure 8 1 Uncap and number 25 HACH vials MB 2 3 4 5 etc 8 2 Turn on COD reactor to infinity to warm up 8 3 Add 2mls of Nanopure to MB vial 1ml of the LCS MS standard to LCS vial 2 0 5ml of the LCS MS standard to the MS and MSD vials and 2mls of the LCS MS standard to the high level LCS vial 8 4 Add 2mls of aqueous sample to corresponding numbered vial Add 1ml of sample chosen for spike if 2mls used to the MS and MSD vials For solid samples weigh out approximately 0 25g of solid sample to the corresponding numbered vial as well as the MS and MSD vials A 1ml autopipetter with the end of the tip clipped off is used for QC samples and samples where 1ml or less is used Use a 5ml autopipetter with the end of the tip clipped off for all other samples Should the analyst feel that the subsample obtained in not a homogenous representative of the original sample due to suspended material that either settles out quickly is too large or does not mix well the TOC Tissue Tearer is used prior to taking a subsample A digested reagent blank used to zero the spectrophotometer must be run for each new lot of Hach tubes This may be kept as long as it is stable Store in a dark place A Revision 5 0 107 COD Page 4 of 7 9 0 Draft method blank that is digested and read must be analyzed once a week and for each new lot of Hach tubes 8 5 If a sample is dirty or turns a greenish color when added to
389. tandard is read for an ICV The results are compared to acceptance ranges 0 1 pH units 97 5 102 5 If the results do not fall within acceptance ranges a new calibration is necessary The pH 7 0 standard is checked at the end of the analysis as a continuing calibration check Results must be within 90 110 for the batch to be acceptable 3 The pH 4 standard is also used as the Lab Control It is analyzed at least once with very analytical batch and at a minimum of once for every 20 samples per matrix type The results are compared to acceptance ranges 0 1 pH units 97 5 102 5 If the results do not fall within acceptance ranges the analysis is considered to be out of control No further samples are analyzed until the out of control situation is corrected Revision 5 0 125 pH Page 6 of 8 10 10 11 4 Initial Demonstration of Capability Prior to analysis of samples or when a significant change is made to the method an Initial Demonstration of Capability Study is performed This is accomplished by analysis of four replicates of a QC sample made at a pH of 4 Acceptance criteria 80 120 maximum RSD of 20 5 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS samples or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance cri
390. te 04 04 06 Revision 7 0 Q01 Page 1 of 14 E S BABCOCK QUALITY CONTROL DATA STANDARD OPERATING PROCEDURE Effective Date 09 08 06 Any regulation or method criteria more stringent than the QC specified here will supercede the following requirements for that particular analysis When methods are analyzed simultaneously the most stringent requirements of the combined methods will be followed If an uncertified matrix is analyzed under a particular method per client request extra QC may not be analyzed for that matrix Normal QC for the certified matrix will validate the batch All QC data is reviewed by the analyst and Peer Reviewer The Supervisor Quality Assurance Manager or other designee may also review the data The following applies primarily to Inorganic and Organic analyses See ESB SOP for microbiology quality control procedures 1 0 Internal Quality Control Note Acceptance Limits Statistical ranges are provided in the LIMS or analytical SOP for all QC samples Limits may be set by the method or generated historically depending on specific method requirements Ranges are monitored regularly by the QA Manager for trends and updated as necessary See ESB SOP Q03 for more details 1 1 Laboratory Control Samples LCS Laboratory Fortified Blanks LFB or Blank Spikes BS 1 1 1 laboratory control is analyzed with each batch of samples or 1 per 20 samples whichever is more frequent and reported per matrix type
391. te stock solution 8 13 1 Sodium salicylate anhydrous 75 g Sodium hydroxide 10 g Dilute to 500 mL with DI water Add 10 g sodium hydroxide pellets to about 400 mL ammonia free water and stir to dissolve Add 75 g sodium salicylate and stir to dissolve Dilute to 500 mL 8 13 5 Store this solution in an opaque bottle Discard if the solution darkens significantly 90 ee AUN 8 14 Sodium hypochlorite reagent 6 15 1 w v Important The bleach should not contain any additives other than NaOCI 8 14 1 Refrigerate this reagent Replace this solution every 4 months 8 14 2 Dilute 10 mL respectively of purchased bleach to 50 mL with D I 8 14 3 Prepare fresh daily Revision 5 0 145 Page 6 of 10 8 15 Stock sodium nitroprusside solution 30 g L 8 15 1 Sodium nitroprusside 3 g 8 15 2 Dilute to 100 mL with DI water 8 15 3 Dissolve 3 g sodium nitroprusside in 100 mL ammonia free water 8 15 4 Store this solution in an opaque bottle in the refrigerator Discard at 6 months or if a blue green tint is seen 8 16 Working salicylate nitroprusside solution 8 16 1 Stock sodium nitroprusside solution above 0 25 mL 8 16 2 Stock sodium salicylate solution above 40 mL 8 16 3 Add 0 25 mL stock sodium nitroprusside solution and 40 mL stock sodium salicylate solution Install the pierced cap and mix gently yet thoroughly over a sink 8 16 4 Replace this reagent wedge monthly Note The above reagent recipes a
392. tected from light at 4 or room temperature Manufacturer expiration dates are observed until vial is opened Once vial is opened standards are kept for up to six months Stock standards can be replaced sooner if comparison with laboratory fortified blanks or QC samples indicate a problem Revision 4 0 O54 8081 Page 6 of 16 541 SURROGATE STANDARD SOLUTION Decachlorobiphenyl is used for the surrogate standard fortifying solution Solutions are stored in sealed vials protected from light at 4 C A 2ppm solution is prepared by diluting 200uL of stock into 100 mL of methanol Solutions are replaced after 6 months or sooner when ongoing QC indicates a problem Spike samples and QC with 150uL for a final concentration of 20ppb in solid samples 60ppb in sludges and 0 3ppb in aqueous samples 5 5 CALIBRATION STANDARDS LABORATORY FORTIFIED BLANK SOLUTION LABORATORY FORTIFIED SAMPLE MATRIX SOLUTION Solutions are stored in sealed vials protected from light at 10 C Intermediate Standard Solutions are replaced after 6 months or sooner if QC samples indicate a problem Working Standards are prepared fresh 5 5 1 Calibration standards are made from a source separate from the LFB LFSM The lowest calibration standard is at or below the method reporting limit The rest of the calibrators bracket the expected working range of the samples Calibration concentrations are 1 25ppb 50ppb 100ppb 250ppb and 500ppb for single peak c
393. ter blank fortified at a concentration of approximately 2 5 times the estimated detection limit To determine MDL values take seven replicate aliquots of the fortified reagent water and process through the entire analytical method Perform all calculations defined in the method and report the concentration values in the appropriate units Calculate the MDL as follows MDL t x S where t students t value for a 99 confidence level and a standard deviation estimate with n 1 degrees of freedom t 3 14 for seven replicates S standard deviation of the replicate analyses See the attached LIMS information for the current MDL study results 9 3 Analyst Demonstration of Capability 9 3 1 9 3 2 Initial Demonstration Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed by each analyst This is accomplished by analysis of four replicates of a QC sample made at a concentration of 1 4 times the RL Concentrations of cation metals may be higher Past studies have been performed at 50 2000ppb The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 20 Demonstration of Continuing Proficiency On an annual basis each analyst must turn in valid LCS data from four consecutive batches or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria
394. teria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year Calculations Reporting 1 Report meter reading in pH units Since all pH readings are taken at 25 C temperature is not reported with the result 2 Report 2 significant figures for all readings below 10 3 significant figures for readings above 213 Even if the electrode with special low sodium error glass is used pH readings between 12 0 to 12 5 may require a correction factor from the attached nomograph See Supervisor to determine if correction is necessary T 3 1 First prescreen the sample to determine if the sodium content is negligible edu 2 A quick conductivity reading will give the analyst a value above the actual sodium content of the sample Although the conductivity reading is not equal to the Sodium concentration we can use the reading as a limit of how high the actual sodium concentration is in the sample T3 Apply the Ec reading in the following fashion on the nomograph Ec reading Na in Molarity 2300 0 1 11 500 05 23 000 1 0 46 000 2 0 Revision 5 0 125 pH Page 7 of 8 115 000 5 0 3 4 If the pH correction to be added is negligible using the above screening steps then the original pH is reported 85 If howe
395. tershed Plan SJR Component The SJR Component is an Integrated Regional Water Management Plan for the San Jacinto River Watershed Funding for this plan will be used to conduct watershed monitoring for the purpose of identifying viable watershed projects The SJRWC has partnered with RCFC and the TASK FORCE among others to conduct these studies The organizational structure of the SJRWC is diagramed in Figure 3 Figure 3 Organizational Chart amp Responsibilities San Jacinto River Component of the Santa Ana Integrated Watershed Plan CA Dept Of Water Resources Grant Manager Natalia Deardorff Santa Ana RWQCB Quality Assurance Pavlova Vitale SJRWC Component Program Administrator Pat Boldt Canyon Lake Monitoring SJR Watershed Monitoring Monitoring Program Manager Program Manager Program Manager Dr Anderson UCR Steve Clark Rick Whetsel Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 9 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Work to be conducted to support the SJR Component Plan by the SJRWC includes monitoring of Canyon Lake as required by the Lake Elsinore and Canyon Lake Nutrient TMDLs This includes in lake water quality monitoring as well as monitoring of sediment re suspension processes to evaluate the applicability of in lake treatment technologies These tasks support the TASK FORCE PROGRAMS and will be considered part of the TASK FORCE PROGRAMS in the remainder of this document Any additiona
396. the Dil column in LIMS See also ESB SOP Q01 for general QC requirements Duplicates are ru The Re TE frequent calculated acceptance limit m analyzed If the the acceptance ra client s results n l h n with every batch or one every ten samples per matrix type whichever is more ative Percent Difference is e RPD does not fall within the aximum of 254 the sample is re RPD still does not fall within ge a note is placed on the A method blank is analyzed with every batch of samples and reported per m atrix type at a minimum of once for every 20 samples Results must be less than 5 mg L and greater than 5 mg L for batch acceptance reporting limit m if the method bla than 1 10 of the sample Blank res to be ND and will not require a n n Sample results at or above the st be accompanied by a qualifier k exceeds a con measured raw con centration greater centration of the lts below the RL are considered A lab control is analyzed with every batch at a minimum of once for every 20 samples and reported Revision 5 0 I31 TSS Page 5 of 6 per matrix type Results must be between 90 110 recovery for batch acceptance If the result falls outside the control limits the analysis is considered to be out of control and all other results in the analytical run are questionable Troubleshooting is pe
397. the QC Office 15 0 References Standard Methods For the Examination of Water and Wastewater 18 Edition APHA AWWA WEF 2540D Methods for the Chemical Analysis of Waters and Wastes EPA 160 2 Note All italicized items are an indication of a variation from the method Revision 45 0 Page 7 of 6 Approved by Susan K Thomas Date I31 TSS 08 10 06 Revision 5 0 I36 Turbidity Page 1 of 7 Standard Operating Procedure Edward S Babcock amp Sons Effective Date 10 06 06 METHOD Standard Methods 2130 B TITLE Turbidity Nephelometric 1 0 Scope and Application This method is applicable to drinking surface and saline waters in the range of turbidity from 0 2 to 4000 nephelometric turbidity units NTU 1 1Health Effects of Turbidity 1 1 1High turbidity levels are often associated with high levels of disease causing microorganisms such as viruses parasites and some bacteria These organisms can cause symptoms such as nausea cramps diarrhea and associated headaches NOTE 1 NTU s are considered comparable to the previously reported Formazin Turbidity Units FTU and Jackson Turbidity Units JTU 2 0 Summary of Method 2 1 The method is based upon a comparison of the intensity of light scattered by the sample under defined conditions with the intensity of light Scattered by a standard reference suspension The higher the intensity of scattered l
398. the instrument you will need to wait for the furnace to heat up and equilibrate to 680 C Select Background Monitor under the Instrument Menu This will show the temperatures and baseline position Exit this menu when the instrument has equilibrated Make sure the hydrator found in the lower right of the instrument is filled with nanopure water NOT the acidified reagent water Check the IC reagent water bottle located on the left of the instrument labeled H3P04 Start the TOC Control program on the PC Connect the instrument by selecting Connect under the Instrument Menu Perform a Residue Removal under Maintenance Menu Ensure that there are bubbles in the IC reaction chamber Load sample table Under Insert select autogenerate and enter 0 20 liquid or 0 20 water in the Method cell Enter the appropriate vial numbers Press the Start button on the computer s TOC Control Panel once the samples have been properly placed on autosampler To view the current results as they are being analyzed select Sample Window under the View Menu Enter the Lab Number in the Sample Number cell Every 15 samples or less you will need to check the 4ppm or 20ppm TOC Standard Every set of 20 or less will need a method blank LCS spike and spike duplicate The spike and spike duplicate is simply 40ul of the LCS intermediate standard in 20ml of sample This will make 4ppm spike It is best that you do a spike on a sample that you know
399. the interference before processing samples Sample results at or above the reporting limit must be accompanied with a qualifier if the method blank exceeds a concentration greater than 1 10 of the measured concentration of the sample Blank results below the reporting limit are considered to be ND and will not require a qualifier 10 3 Laboratory Demonstration of Capability 10 3 1 Prior to initial analysis of samples or when a significant change is made to the method a Demonstration of Capability Study is performed Select a concentration 10 50 times the estimated MDL or midrange and analyze 4 aliquots For aqueous studies spike the selected concentration in reagent water and for non aqueous studies spike in sodium sulfate Analyze each aliquot according to procedures beginning in Sect 11 A cell change may be performed in lieu of an IDOC See ESP SOP QOI 10 3 2 For each analyte the mean recovery value of four of these samples must fall in the proper acceptance range For aqueous samples 70 13096 with a RSD 20 For poorly performing analytes the criteria from Table 6 of EPA Method 8141B Rev 2A is utilized For analytes not found in Table 6 the range is set to equal that Revision 4 1 Page 11 of 16 10 4 10 5 10 6 10 7 O53 8141 of a similar poor performing analyte For nonaqueous samples 70 13096 with a RSD 2096 For poorly performing analytes the criteria from Table 7 of EPA Method 8141B Rev 2A is utilized F
400. the responses is not within the 15 check the instrument operating conditions if necessary restore them to the original settings and inject another aliquot of the calibration verification standard If the average response still exceeds 15 a new calibration is performed 7 4 3 4 A standard at the reporting limit is analyzed at the end of the run or after every 20 samples This is used to evaluate instrument sensitivity should calibration checks show a low bias This standard should have a signal greater then the method blank Retention time windows Absolute retention times are used for compound identification Retention time windows are crucial to the identification of target compounds 7 4 1 1 Before establishing the retention time windows make sure the gas chromatographic system is operating within optimum conditions 7 4 1 Retention time window studies are performed as stated in Method 8000 section 7 6 Windows are set per analyte per analyst discretion The experience of the analyst weighs heavily in the interpretation of chromatograms Each analyte in each standard must fall within its respective retention time window If not the gas chromatographic system must either be adjusted so that a second analysis of the standard does result in all analytes falling within their retention time windows or a new initial calibration is performed and new retention time windows established Inject a 2 uL aliquot of the concentrated sample e
401. this is not possible qualify the surrogate compounds with QFspk for QC surrogates and NSspk for sample surrogates If surrogate recovery is unacceptable the sample must be re extracted assuming enough sample is available Whenever possible re extractions are performed within the holding time However they may be performed past the holding time since the reanalysis is to confirm if matrix interference is present The original result bearing a confirmed qualifier NSdup is reported to the client unless the follow up Revision 7 0 006 Page 9 of 11 6 5 6 6 shows it to be erroneous If the reanalysis is reported it must be accompanied with the proper qualifier N_HTc clearly stating that it was analyzed past the regulatory holding time If re extraction is not possible or if re extraction does not correct the problem results must be accompanied by the proper qualifier on the surrogate compound NSdup NShi NSlo if management deems the sample reportable On QC samples if some of the surrogates are out but it is still considered acceptable based on the above criteria use the qualifier QSpas on the surrogate compound that is out If surrogate recovery is not acceptable on a QC sample use QSout on the surrogate compound that is out Surrogate failures on QC samples do not make the QC of control Percent recovery and RPD alone are used to determine QC sample acceptability unless otherwise specified in the method SOP How
402. tial Field Preservation Holding Time Volume days turbidity SM2130B 1 Quart Quart Poly Unpres 2 water temperature SM 2550B N A N A SM4500 pH H4B 1 Quart Quart Poly Unpres 1 total organic nitrogen Org N CALC N A N A N A N A nitrite nitrogen NO2 N 1 Quart Quart Poly Unpres 2 nitrate nitrogen NO3 N EPA 300 0 1 Quart Quart Poly Unpres 2 ammonia nitrogen NH4 N on 1 Quart Quart Poly H2S04 28 total phosphorus TP as 1 Quart Quart Poly 2504 28 soluble reactive phosphorus SM4500 P SRP ortho P 1 Quart Quart Poly Unpres 2 total suspended solids TSS SM2540C 1 Quart Quart Poly Unpres 7 GOD oxygen demand SM5220D 1 Quart Quart Poly H2S04 28 oo oxygen demand 91452108 1 Quart Quart Poly Unpres 2 total nitrogen TN CALC N A N A N A N A total dissolved solids TDS SM2540D 1 Quart Quart Poly Unpres 7 total Kjeldahl nitrogen TKN EPA 351 2 500 mL 500 mL Poly H2S04 28 E coli SM9221 E 125 mL 125 mL Sterile Na2S203 0 25 total arsenic AStotai EPA 200 8 500 mL 500 mL Poly HNO3 180 total cadmium EPA 200 8 500 mL 500 mL Poly HNO3 180 total copper Cutotal EPA 200 8 500 mL 500 mL Poly HNO3 180 total lead EPA 200 8 500 mL 500 mL Poly HNO3 180 total zinc Znioiai EPA 200 8 500 mL 500 mL Poly HNO3 180 total chromium Crioia EPA 200 8 500 mL 500 mL Poly HNO3 180 total mercury Hgiotai EPA 200 8 500 mL 500 mL Poly HNO3 28 organochlorine OC pesticides EPA 8081 3L p s Unpreserved 7 Aldrin OC EPA
403. time for this sample should be the same as a normal sample analysis period followed by analysis of the rinse blank at designated intervals The length of time required to reduce analyte signals to less than one half the reporting limit is applied If one half the reporting limit is less than the MDL signals must be less than the MDL When there is suspected additional memory interference between samples the rinse cycle is repeated and the sample is reanalyzed The toxicity or carcinogenicity of chemicals used in this method has not been precisely defined Each chemical should be treated as a potential health hazard and exposure to these chemicals should be minimized A reference file of material data handling sheets is made available to all personnel involved in the chemical analysis See SOP S01 Concentrated Acids and Bases SOP S02 Compressed Gas Cylinder Handling SOP S03 Spill Control Policy General laboratory safety procedures are sufficient for this analysis Recommended safety equipment includes gloves and safety glasses 6 0 EQUIPMENT AND SUPPLIES 6 1 Inductively coupled plasma emission spectrometer Perkin Elmer Optima 5300DV Computer controlled emission spectrometer with background correction capability 6 1 1 6 1 2 Radio frequency generator compliant with FCC regulations per PE manual Argon gas supply High purity grade 99 99 When analyses are conducted frequently liquid argon is more economical
404. tion 1 1 This method includes the measurement of organic carbon in drinking surface and saline waters domestic and industrial wastes Since the sample is purged to remove inorganic carbon the result is essentially nonpurgeable organic carbon See Definitions and Interferences for other exclusions 1 2 The method is applicable to measurement of organic carbon for aqueous sample from 0 3 for waters and 0 7 for liquids to 20mg L 1 3 This method may also be used for solid samples if both client and regulator agree to this variation Range 0 296 to 3 2 Carbon 2 0 Summary of Method 2 1 Organic carbon in a sample is converted to carbon dioxide CO2 by catalytic combustion The CO2 formed can be measured directly by an infrared detector The amount of CO2 is directly proportional to the concentration of carbonaceous material in the sample 3 0 Definitions See also SOP Q15 3 1 The carbonaceous analyzer measures all of the carbon in a sample Because of various properties of carbon containing compounds in liquid samples preliminary treatment of the sample prior to analysis dictates the definition of the carbon as it is measured Forms of carbon that can be measured by the method are 3 1 1 soluble nonvolatile organic carbon for instance natural sugars 3 1 2 soluble volatile organic carbon for instance mercaptans 3 1 3 insoluble partially volatile carbon for instance oils 3 1 4 insoluble particulate carbonaceous materials for inst
405. tion volumes Sludge MDLs are then calculated by applying a preparation factor to the solid MDL Results must be below the reporting limit for Inorganic analyses or 2 2 times the reporting limit for Organic analyses If the MDL is greater then the reporting limit but within the 2 2 times criteria for Organic analyses the MDL will be entered into LIMS as equivalent to the RL or if possible the RL will be raised An analyst may exclude a data point from the study as long as it is proven to be a statistical outlyer This is determined using the Grubbs Test A 9596 confidence level is used to determine if a data point may be rejected The analyst must document this proof with the raw data All data is reported from the primary column or detector Method MDLs may be set equal to or greater than the statistically derived MDL Often it is set at 1 2 the reporting limit or 2 2 times the statistically derived MDL If an analysis is performed on more than one instrument or column the higher of the two MDLs is generally entered as the default value into LIMS New MDLs are entered into the LIMS system The RL date is changed to reflect the date of entry All versions of analyses may be updated from the Master or primary analysis with the following exceptions 4 6 1 UCMR ML and SIM products have specific RLs and MDLs 4 6 2 CAM and TCLP analyses have RLs that relate to the regulatory limits See ESB SOP E01 and E02 4 6 3 Client products may h
406. tions The following solutions are stored at 4 C Intermediate standards and 70 C Working standards for up to 6 months Standards will be replaced sooner if comparison with QC samples indicate a problem 7 4 1 Internal Standard Solution The internal standard solution is 500ppm solution of Triphenylphosphate TPP purchased from Ultra Scientific No dilution is made Spike 8uL of the 500ppm stock Internal Standard solution into 1mL of sample extract for a final concentration of 4ppm in the extract Surrogate Standard Solution The surrogate standard solution is a 250ppm solution of 3 dimethyl 2 nitrobenzene purchased from Ultra Scientific Manufacturer expiration dates are observed and the standard should be replaced when ongoing QC indicates a problem No dilution is made Samples are spiked with 100uL of this 250ppm standard which results in a concentration of 25ppb in the sample and 5000ppb in the extract Calibration Standards primary source A five point calibration is required for a linear first order model six point calibration for a quadratic second order model and seven point for a polynomial third order model Six standards are purchased from Ultra Scientific 7 4 2 7 4 3 SPM 824 Azinphos Methyl Diazinon Fenthion Phorate Bolstar Dichlorvos Merphos Ronnel Chlorpyrifos Disulfoton Methyl Parathion Stirofos Coumaphos Ethoprop Mevinphos Tokuthion Demeton Fensulfothion Naled Trichloronate SPM 834 Dimethoat
407. tivation solution rinse the injector body with toluene methanol acetone then hexane Reassemble the injector and replace the columns 7 6 3 Column rinsing The column should be rinsed with several column volumes of an appropriate solvent Both polar and nonpolar solvents are recommended Depending on the nature of the sample residues expected the first rinse might be water followed by methanol and acetone Methylene chloride is a good final rinse and in some cases may be the only solvent required The column should then be filled with methylene chloride and allowed to stand flooded overnight to allow materials within the stationary phase to migrate into the solvent The column is then flushed with fresh methylene chloride drained and dried at room temperature with a stream of ultrapure nitrogen 8 0 QUALITY CONTROL Note See also ESB SOP 01 for general QC requirements 8 1 Minimum quality control QC requirements are initial demonstration of laboratory capability determination of surrogate compound recoveries in each sample and blank analysis of laboratory reagent blanks laboratory fortified samples laboratory fortified blanks and PT samples Revision 4 0 Page 14 of 16 O54 8081 8 2 Laboratory Reagent Blanks Before processing any samples the analyst must demonstrate that all glassware and reagent interferences are under control Each time a set of samples is extracted or reagents are changed a laboratory reagent blank
408. tock standards can be replaced er if comparison with QC samples indicate a lem Once opened the expiration date is 1 year date opened as long as this does not exceed manu sour prep veri facturer s original expiration date Two ces are purchased one for calibration standard aration and the second source for calibration 6 3 Stan fication LCS preparation dard formazin turbidity suspension prepared 6 3 1 LCS Prepare daily as specified below for from noncalibration stock source 6 3 2 Calibration Standards Prepare each time a calibration is necessary as specified below for instrument calibration Revision 5 0 Page 4 of 7 For Standard Concentration NTU NANOPURE 4000 1000 800 400 200 80 40 20 8 4 0 85 Pipette mls From Stock fill cell 25 20 10 5 2 al 2 0 2 0 05 NTU is added from the dilution water 7 0 Procedure 7 1 Turbidimeter calibration I36 Turbidity Dilute To Vol ume in mls with 100 100 100 100 1000 1000 1000 The manufacturer s operating instructions are followed which specify calibration every 90 days for USEPA reporting However Photo should the Electronic P C Board the Detectors or the Light Source b replaced or if very carefully prepared Formazine Suspensions indicate a need for recalibration this often done mor 7 2 Calibration 7 2 1Always mix the contents of each c
409. tory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 20 Performance Evaluation Studies are performed twice a year 13 0 Calculations 14 15 16 Data 17 0 0 0 0 13 1 Calculate the answer as follows 1413 Sample Reading pmho s X Standard Reading pmho s Reporting 14 1 Conductivity is reported as umhos cm Since all EC readings are taken at 25 temperature is not reported with the result 14 2 The reporting limit is 1 0 pmho cm 14 3 Report the result as 2 significant figures for all answers under 1000 Above 1000 3 significant figures are reported If EC is gt 5000 pmhos cm please note this in Sample Comments in Element Update Status Definitions See SOP Q15 SOP Definitions Corrective Action For Out of Control or Unacceptable See SOP Q06 Corrective Action Pollution Prevention and Waste Management See SOP S07 Pollution Prevention Revision 5 0 114 EC Page 7 of 7 References Method Source EPA 120 1 Methods for Chemical Analysis of Water and Wastes Standard Methods for the Examination of Water and Wastewater AWWA APHA WPCF 18th edition 2510B Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 10 30 06 Revision 7 0 Page 1 of 15 119 Anions Standard Operating Procedure Edward S
410. total chromium total dissolved solids TDS total mercury total arsenic Asia organochlorine pesticides total cadmium organophosphate pesticides Furthermore each dump site will be characterized as to size and ownership public private of parcel likely access point s impacted threatened or endangered species habitat and description of impacted or threatened receiving waters Aerial Photography Based on historical research and active dump sites identified above an approximate one square mile sub area where illegal dumping activities are prevalent will be selected within the project area for surveillance monitoring via aerial photography Up to four photo flights will be conducted on the sub area A flight will be conducted at the beginning and end of the grant project Up to two additional flights will be conducted if needed The aerial flights will be using high resolution photography taken to a scale of at least one inch equals two hundred 200 feet The RCFC s photogrammetry section will prepare and conduct via contract the photographic documentation Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 18 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Trash Clean Up Events Records will be kept consistent with Riverside County Environmental Health protocols of materials deposited at trash clean up events sponsored by the grant project Chemi
411. trol programs for the inspection of supplies and consumables in accordance with their SOPs which include those specified by the manufacturer and those specified by the method Laboratories are required to submit a copy of their SOPs for inspection of supplies and consumables to the TASK FORCE Quality Assurance Manager for review and approval Please refer to the report Appendices A amp B for available laboratory SOPs B9 NON DIRECT MEASUREMENTS The only non direct measurements used within the Lake Elsinore and Canyon Lake Nutrient TMDL monitoring program are from databases maintained by the TASK FORCE or from prior studies The database is maintained in accordance with TASK FORCE policy as stated earlier The data will be reviewed against the data quality objectives stated in Section A7 and only that data meeting all of the criteria will be used in this project Other items within the non direct measurement component are not applicable to the TMDL Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 38 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE B10 DATA MANAGEMENT Data will be maintained as established in Section A9 The TASK FORCE will maintain an inventory of data and its forms and will periodically check the inventory against the records in their possession Data samples will be collected according to the procedures outlined in Section B1 Sampling Process Design Field measurements will be recorded on standard Field Log
412. turer expiration dates are observed 8 2Reagent water D I water 9 0 Procedure Revision 5 0 125 Page 3 of 8 9 1 The pH electrode should be hooked up to the Specific ion meter on the back of the black box 9 2Set the specific ion meter dial to pH mode 9 3Rinse the electrode with the D I wash bottle and dry the electrode 9 4Pour all the samples and standards in test tubes fill to 4 of the volume and place in the water bath at 25 C 9 5 Calibration Calibrate the specific ion meter on Standard buffers of pH 7 and 10 as specified by the manufacturer Check the calibration by reading the Standard pH 4 buffer The probe is not placed in successive portions of buffer solution as specified in the method however if unusual variations are observed buffer solutions are repoured and reanalyzed 9 5 1 Press down on calibrate one Place the clean electrode in Standard buffer pH 7 Wait until the green ready light appears making sure to allow sufficient time for settling Set the reading to 7 Press lt ENTER gt 9 5 2 Take the electrode out of the standard rinse and dry the electrode and then place it in Standard buffer pH 10 Wait until the ready light appears on calibrate 2 Set the reading to 10 press lt ENTER gt 9 5 3 Take the electrode out rinse it with the D I wash bottle dry and place it in Standard buffer pH 4 which is also the LCS The green light should now be on sample and
413. ty Assurance Managers may stop all actions including those conducted by any contracting laboratory if there are significant deviations from required practices or if there is evidence of a systematic failure QAPP Update and Maintenance Changes and updates to this QAPP may be made after a review of the evidence for change by the TASK FORCE Technical Advisory Committee SJRIPP Monitoring Program Manager TASK FORCE Monitoring Program Manager and with the concurrence of both the Santa Ana Regional Board s TMDL Program Manager and Quality Assurance Program Manager listed in Table 1 The SJRIPP Monitoring Program Manager may amend those portions of the QAPP specific to the SJRIPP with the concurrence of both the Santa Ana Regional Board s TMDL Program Manager and Quality Assurance Program Manager The TASK FORCE and SJRIPP Monitoring Program Managers will communicate to ensure that all revisions are fully incorporated into all applicable monitoring programs The Quality Assurance Managers will be responsible for making the changes submitting drafts for review preparing a final copy and submitting the final for signature Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE Page 10 Table 1 Responsible Personnel QAPP Update and Maintenance Organizational Contact Information Tele Fax e Name Hue Title Affiliation mail Mark Norton Lake Elsinore amp
414. uirements of this program are stipulated below 10 1 1 In recognition of the rapid advances occurring in chromatography the analyst is permitted certain options to improve the separations or lower the cost of measurements Each time such modifications to the method are made the analyst is required to repeat the procedure in Section 10 2 10 2 Initial Demonstration of Proficiency Before performing any analyses the analyst demonstrates the ability to generate acceptable accuracy and precision with this method 10 2 1 Each analyst will analyze four replicates of a standard at the NELAP level of 1 4x RL The average percent recovery of the QC samples must be 80 120 with a maximum RSD of 10 10 3 Demonstration of Continuing Proficiency On an annual basis analyst must turn in valid LCS data from four consecutive LCS s or results from a successful Performance Evaluation Study LCS percent recovery must meet laboratory prescribed acceptance criteria Relative standard deviation between the four replicates must be less than or equal to 2096 Performance Evaluation Studies are performed twice a year or more Quality control check samples are analyzed twice a year with the performance evaluation sample studies required to maintain state certification Study limits are used to evaluate results 10 4 Calibration Blank Method Blank 10 4 1 An aliquot of Nanopure water is analyzed at the beginning of each run every ten samples and at the end of the
415. up on tape on a weekly basis as part of SAWPA s SOP for disaster recovery Back up tapes are kept for a minimum of four weeks before they are written over Tapes are rotated off site for separate storage on a monthly or more frequent basis in accordance with SAWPA Information Systems SOPs Each back up session validates whether the files on tape are accurate copies of the original The TASK FORCE also maintains an access log showing who accessed the database when and what was done during the session AII changes to the database are stored in a transaction database with the possibility of rollback if necessary Data will be stored on a Windows 2003 Server with a 2Ghz CPU and 2Gb RAM with a fail safe RAID 5 configuration The server checks for operating system updates daily and downloads and installs patches and service packs as necessary The current server is two years old and as per SAWPA policy will be replaced after a maximum of 4 years of service The server is also protected with Norton Anti Virus software which is updated daily The database software is Microsoft SQL Server 2000 standard edition with Service Pack 4 The database administrator checks the Microsoft Website for new patches and service packs on a monthly basis and installs updates as necessary The general policy for updating operating system and database software is to evaluate the software on a test machine after a new version has been out for approximately 1 year The new ver
416. using manufacturer specified holding times Once a stock standard is opened the expiration date is one year as long as this date does not exceed the original manufacturer s date and percent recovery is acceptable 7 1 2 LCS Dilute 50 uL of stock standard 7 1 1 to 50 ml of diluant 6 2 The concentration is 1 mg L NH3 or 0 78 mg L NH3 N This solution is stored at 4 for up to 2 weeks 7 1 3 A LCS is analyzed for every 20 samples per matrix type or one per analysis batch whichever is greater LCSs are distilled unless the sample batch contains only undistilled samples 7 1 4 Ifthe LCS analysis does not fall within the acceptance range of 90 110 the analysis is stopped until the cause is determined and the LCS is within the acceptance range 7 2 Matrix Spike MS Matrix Spike Duplicate MSD 7 2 1 Spike solution Spike 50uL of stock standard 7 1 1 into 50 ml of sample The spike concentration is 1 mg L NH3 or 0 78 mg L NH3 N 7 2 2 A MS MSD is analyzed for every twenty samples per matrix type or one per analysis batch whichever is greater Spikes are distilled unless the sample batch contains only undistilled samples 7 2 3 Acceptability Acceptance ranges are 80 120 recovery with a maximum RPD of 20 7 3 Method Blank 7 3 1 Use diluant from section 6 2 7 3 2 A MB is analyzed for every twenty samples per matrix type or one per analysis batch whichever is greater and reported per matrix type Blanks are distilled unless
417. va Vitale Santa Ana Regional Quality Assurance 951 782 4920 Water Quality Control Program Manager 951 782 6288 fax Board pvitale waterboards ca gov Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Page 11 Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE A5 PROBLEM DEFINITION AND BACKGROUND Lake Elsinore lies approximately 60 miles southeast of Los Angeles and 22 miles southwest of the City of Riverside The Lake is located within the City of Lake Elsinore in Riverside County and is a natural low point of the San Jacinto River and its drainage basin The total drainage basin of the San Jacinto River Watershed is approximately 782 square miles Over 90 percent of the watershed 735 square miles drains first into Railroad Canyon Reservoir also known as Canyon Lake which in turn flows into Lake Elsinore the terminus of the San Jacinto River Watershed The local tributary area to Lake Elsinore consisting of drainage from the Santa Ana Mountains to the west and the City of Lake Elsinore is approximately 47 square miles In 1994 1998 and again in 2002 Lake Elsinore and Canyon Lake were identified by the California Regional Water Quality Control Board Santa Ana Region Regional Board on its Clean Water Act Section 303 d list of impaired waters Impairments identified for these waters included excessive levels of nutrients in both lakes as well as organic enrichment low dissolved oxygen sedimentation si
418. valuate the data with this concern in mind and rerun any samples the may have been affected by carry over 4 3 Matrix interferences may be caused by contaminants that are coextracted from the sample Also note that all the analytes listed in the scope and application section are not resolved from each other on any one column i e one analyte of interest may be an interferant for another analyte of interest The extent of matrix interferences will vary considerably from source to source depending upon the water sampled Further processing of sample extracts may be necessary Positive identifications are confirmed by GCMS 4 4 It is important that samples and working standards be contained in the same solvent The solvent for working standards must be the same as the final solvent used in sample preparation If this is not the case chromatographic comparability of standards to sample may be affected 4 5 Analytical difficulties encountered for target analytes include 4 5 1 Tetraethyl pyrophosphate TEPP is an unstable diphosphate which is readily hydrolyzed in water and is thermally labile TEPP decomposes at 170 C Care must be taken to minimize loss during GC analysis and during sample preparation Identification of bad standard lots is difficult since the electron impact EI mass spectrum of TEPP is nearly identical to its major breakdown product triethyl phosphate 4 5 2 The water solubility of Dichlorvos DDVP is 10g L at 20 a
419. vatives Analysis Requested DW Drinking Water WW Wastewater GW Groundwater S Soil SG Sludge Total of Containers SS SS Employer Signature o I D Unpreserved H2504 Sample ID Awa Relinquished Print Name Compan Date Time Burg 7j 8 i 1 RL q By sign hn EU pes a ee jt y Fs Ete ur of Lake Elsinore amp Canyon Lake Nutrient TMDL QAPP Lake Elsinore amp Canyon Lake Nutrient TMDL TASK FORCE APPENDIX A E S BABCOCK AND SONS INC LABORATORY STANDARD OPERATION PROCEDURES Revision 3 0 06 Page 1 of 8 Sample Splitting Preservation Storage and Disposal Edward S Babcock amp Sons Standard Operating Procedure Effective Date 09 08 06 1 0 following procedures are in place to safeguard samples from deterioration contamination loss or damage 2 0 1 samples must be thoroughly mixed prior to removing subsamples Please be aware of client id and special instructions in the comments Once a sample is preserved or split wrong it cannot be fixed so be careful 3 0 sample preservation and screening is noted on the Work Order Printout 3 1 Samples that are received preserved are checked for proper pH If more preservative is required a is written next to the preserved bottle listed on the Work Order Printout 3 2 Samples that are received unpreserved may
420. ver the pH correction to added does change the original pH reading an actual sodium content must be determined by the ICP Once this value is obtained convert the mg L result to molarity and find the actual pH correction to be added value from the nomograph Conversion to molarity Na in mg L mime Molarity of Na 23 000 4 For sample readings below 1 report 1 in the text field 2D For sample readings above 14 report gt 14 in the text field 12 0 Definitions See SOP 015 SOP Definitions 13 0 Corrective Action For Out of Control or Unacceptable Data 1 37 0 See SOP 006 Corrective Action 14 0 Pollution Prevention and Waste Management 14 1 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes 14 2 See SOP 507 Pollution Prevention References Method Source Standard Methods for the Examination of Water and Wastewater AWWA WPCF 18th edition 4500 H B EPA 9040B 9045C Methods for the Chemical Analysis of Waters and Wastes Revision 5 0 125 Page 8 of 8 Note All italicized items are an indication of a variation from the method Approved by Susann K Thomas Date 10 30 06 Revision 5 0 I27 OP Page 1 of 9 ORTHO PHOSPHATE PHOSPHORUS Edward S Babcock amp Sons STANDARD OPERATING PROCEDURE ASCORBIC ACID METHOD SM 4500 P E Effective Date 082806 1 0 Scope and Application This m
421. window size for a compound or a percentage RT window approximating the 3 however the experience of the analyst weighs heavily in the interpretation of chromatograms If this window is too narrow the lab uses 30sec with MS confirmation See Method 8000 section 7 6 for retention time study details 12 3 Identification requires expert judgement when sample components are not resolved chromatographically When peaks obviously represent more than one sample component i e broadened peak with shoulder s or valley between two or more maxima or any time doubt exists over the identification of a peak on a chromatogram appropriate alternative techniques to help confirm peak identification are employed See EPA method 8141B section 3 8 for a discussion concerning analytical difficulties for specific analytes Coeluding analytes can be identified separately by the MS If both analytes appear to be present based on the MS evaluation quantification is done by applying a ratio derived from the MS response to the sample result Revision 4 1 Page 14 of 16 13 0 CALCULATIONS O53 8141 13 1 Calculate analyte concentrations in the sample from the response for the analyte using the calibration procedure described in Sect 9 13 2 Ifthe internal standard calibration procedure is used calculate the concentration C in the sample using the response factor RF determined in Sect 9 2 and Equation 2 or determine sample concentration from the cal
422. xtract Record the resulting peak height or area Tentative identification of an analyte occurs when a peak from a sample extract falls within the absolute retention time window results are reported from the primary column and confirmed using the secondary column unless analytical conditions and quality control samples indicate that the secondary column results are more accurate See ESB SOP Q20 for details The primary column for all of Revision 4 0 Page 11 of 16 7 4 8 O54 8081 the analytes specified in section 1 1 and 1 6 is column A If in any case the secondary column is used for quantification the analyst will document her reasoning for doing so When using the external calibration procedure determine the quantity of each component peak in the sample chromatogram that corresponds to the compounds used for calibration purposes as follows Proper quantitation requires the appropriate selection of a baseline from which the peak area or height can be determined 7 4 8 1 For aqueous samples Ax VOCD Concentration ug L CF Vi Vs where Ax Area or height of the peak for the analyte in the sample Vt Total volume of the concentrated extract uL D Dilution factor if the sample or extract was diluted prior to analysis If no dilution was made D 1 The dilution factor is always dimensionless CF Mean calibration factor from the initial calibration area ng Vi Volume of the extra
423. y result may be reported with a qualifier 4 5 Organic analyses with gt seven analytes 4 5 1 4 5 2 4 5 3 4 5 4 Analytes appearing in the calibration standards that are not part of the LIMS reporting lists will be noted with parentheses as nontarget analytes These analytes are not evaluated for calibration acceptance since their results are not reported to clients If a special request is made to report these analytes then calibration acceptance will be evaluated If all of the individual target analytes do not meet calibration acceptance criteria a calibration may be accepted if the mean of the RSD values of all analytes target and nontarget in the calibration is lt 20 If mean criteria is used instead of individual RSD or coefficients reportable results must be qualified for analytes outside original method criteria If the mean is not acceptable then a new calibration must be made before sample analyses If the ICV average is unacceptable the system must be recalibrated If any samples were analyzed they must be rerun An ICV is acceptable if the average of all the ICV analyte responses recovery or difference between calibration average RF and ICV RF is within 85 115 acceptance criteria or if every individual target analyte meets method acceptance criteria specified in the SOP 4 5 4 1 Individual analytes falling outside the acceptance criteria must be noted on the analyst s run 4 5 4 2 If analyte average is used
424. ying oven overnight 6 5 Labels 6 6 365 nm Fluorescent light 6 7 Water bath at 44 5 C 0 2 6 8 Incubators at 35 0 5 7 0 Reagents and Standards 7 1 Lauryl Sulfate Broth Brilliant Green Bile EC Media and 7 1 1 Weekly Preparation 7 1 1 1 Directions on media labels are followed for proper rehydration 7 1 1 1 1 LSB 356g media for every 5 liters of Nanopure 7 1 1 1 2 BGB 120g media for every 3 liters of Nanopure 7 1 1 1 3 EC 166 5g media for every 4 5 liters of Nanopure 7 1 1 1 4 MUG 111g media for every 3 liters of Nanopure Revision 6 0 Page 3 of 9 7 2 7 3 7 4 7 5 B02 MTF 7 1 1 2 Lauryl Sulfate Broth is rehydrated at double strength with Nanopure water as indicated in Standard Methods when used with 10 mL aliquots of sample 10 milliliters of the rehydrated medium is added to each test tube along with an inverted Durham tube which sits inside the medium tube A loosely fitting lid is then added to each test tube before it is autoclaved 7 1 1 3 Prepared media is autoclaved for 12 15 minutes at 250 121 C and 15 Ib in2 pressure 7 1 1 4 sterilized media is stored for later use in a cool cabinet out of direct sunlight with loose fitting caps for up to two weeks A previous study showed that evaporation of media does not exceed 1 mL until 3 months have elapsed Each rack of media is identified and dated and rotated to ensure the oldest media is used first Tubes stored longer t
425. ys Nitrate N Nitrite N Unchlorinated Cool to 4 C 48 hours chlorinated Cool to 4 C 14 days combined conc HSO pH 2 28 days o Phosphate P Cool to 4 C 48 hours Sulfate Cool to 4 C 28 days PCBSA Cool to 4 C 28 days 8 3 method of preservation and the holding time for samples analyzed by this method are determined by the anions of interest In a given sample the anion that requires the most preservation treatment and the shortest holding time will determine the preservation treatment It is recommended that all samples be cooled to 4 C and held no longer than 28 days If a preserved sample is used it must be neutralized prior to injection 9 0 Calibration and Standardization Revision 7 0 119 Anions Page 6 of 15 9 1 Calibrators at three levels are required for each analyte of interest Generally calibration standards are prepared at eight concentration levels by adding accurately measured volumes of one or more stock standards to a volumetric flask and diluting to volume with reagent water as specified in section A quadratic curve fit is used The curve is forced through the zero point 9 5 4 9 2 An acceptable curve has an r 0 99 A method blank is analyzed after the calibration to verify the zero point since method software will not allow a blank to be quantified as part of the calibration 9 3 Using 25 uL injections of each calibration standard tabulate peak height or area responses against the concentration Th
426. yses provide an indication of the quality of the sample data and should be provided with the sample results at the time of LIMS entry 13 METHOD PERFORMANCE See Initial Demonstration of Proficiency report prepared for this method 14 CORRECTIVE ACTION FOR OUT OF CONTROL UNACCEPTABLE DATA See SOP Q06 Corrective Action 15 POLLUTION PREVENTION AND WASTE MANAGEMENT 15 1 Waste Disposal 15 1 1 Instrument waste is placed in the Low Concentration Acid Waste Drum 15 1 2 Digests are placed in the High Concentration Acid Waste Drum 15 1 3 Preserved samples are placed Low Concentration Acid Waste Drum 15 1 4 Expired standards are placed in the High Concentration Acid Waste Drum 15 1 5 Expired Hg standards are placed in the COD Waste Drum 15 2 See SOP S05 Neutralization Procedure for Acid and Alkaline Wastes SOP S07 Pollution Prevention REFERENCES EPA Method 200 8 Supplement I May 1994 Note All italicized items are an indication of a variation from the method Revision 3 0 Page 21 of 26 MI2 200 8 TABLES DIAGRAMS FLOWCHARTS AND VALIDATION DATA TABLE 2 COMMON MOLECULAR ION INTERFERENCES IN ICP MS 52 76 78 Sc Cr Cr Mn Se Se Se Molecular Ion Mass 15 17 2 18 2 24 CN 26 CO 28 N2 28 N2H 29 NO 30 NOH 31 O2 32 02H 33 36ArH 37 38ArH 39 40ArH 41 2 44 CO2H 45 ArC ArO ArN 54 ArNH 55 ArO 56 ArOH 57 40Ar36Ar 40Ar38Ar 40 2 80

San Jacinto QAPP

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